WO2012133717A1 - Ethylene-based polymer, polyethylene resin composition and use thereof, catalyst ingredient for olefin polymerization, catalyst for olefin polymerization containing said ingredient, and process for producing ethylene-based polymer using said catalyst - Google Patents

Ethylene-based polymer, polyethylene resin composition and use thereof, catalyst ingredient for olefin polymerization, catalyst for olefin polymerization containing said ingredient, and process for producing ethylene-based polymer using said catalyst Download PDF

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WO2012133717A1
WO2012133717A1 PCT/JP2012/058491 JP2012058491W WO2012133717A1 WO 2012133717 A1 WO2012133717 A1 WO 2012133717A1 JP 2012058491 W JP2012058491 W JP 2012058491W WO 2012133717 A1 WO2012133717 A1 WO 2012133717A1
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carbon atoms
ethylene
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hydrocarbon group
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由之 石濱
亮介 浅川
努 櫻木
福田 哲朗
坂田 和也
勝 青木
健二 河岸
圭一 吉本
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日本ポリエチレン株式会社
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    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L23/08Copolymers of ethene
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    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
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    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
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    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L2314/06Metallocene or single site catalysts

Abstract

The purpose of the present invention is to provide: a polyethylene resin composition which has excellent moldability and from which molded objects that are excellent in terms of balance between impact strength and rigidity and of transparency can be produced; and a molded object and a film which are obtained by molding the polyethylene resin composition. This polyethylene resin composition comprises 41-99 wt.% ethylene-based polymer (A) which satisfies specific requirements and 1-59 wt.% ethylene-based polymer (B) which satisfies specific requirements, the composition as a whole having an MFR of 0.05-50 g/10 min and a density of 0.910-0.960 g/cm3.

Description

Ethylene polymer, method for producing a polyethylene resin composition and uses thereof, olefin polymerization catalyst components, olefin polymerization catalyst and the ethylene polymer using the catalyst containing the components

The present invention relates to ethylene polymer having excellent moldability which has a long-chain branched structure developed. Further, as another aspect of the present invention, the present invention relates to a novel polyethylene resin composition and use thereof, and more particularly, excellent in moldability, and an excellent balance and transparency of impact strength and rigidity molded polyethylene resin composition capable of producing a body, and injection molding the polyethylene resin composition, compression injection molding, rotational molding, extrusion molding, a molded body and a film obtained by blow-molding or blow molding. The invention further olefin polymerization catalyst component containing a specific metallocene compound, a process for producing an olefin polymer using the olefin polymerization catalyst and the catalyst comprising the components.

Recently, in various industrial fields, plastic film, sheet, injection molded articles, pipes, extrudates, now hollow molded body or the like is actively used. Particularly inexpensive, lightweight, moldability, rigidity, impact strength, transparency, chemical resistance, polyethylene resin (ethylene polymer) is used widely because of such excellent recyclability. Generally, molding of the polyethylene resin is carried out in the molten state. However, in the case of a single ethylene polymer, its melting characteristics, for example, or insufficient in terms of fluidity, elongational viscosity and or insufficient, to ensure sufficient formability or difficult, often solid properties such as transparency and rigidity or insufficient.

As a measure to compensate for these, or a blend of high-pressure polyethylene (HPLD) having excellent formability, or by blending the different ethylene polymer molecular weight and density, it is carried out improvement in melt properties and solid properties and have (e.g., see Patent documents 1-3).
However, in these blends (ethylene-based resin composition), although moldability is obtained, or cause a decrease in impact strength due to blending of HPLD, transparency by the molecular weight distribution and the copolymer composition distribution becomes wider there is a problem or to deteriorate.

Further, in view of the need to reduce the raw material resin usage in modern container recycling law enforcement and resource saving flow, but there is an increasing demand for thinning of the molded body, for this purpose, the rigidity with impact strength it is necessary to improve the (elastic modulus).
As a method for improving the impact strength, a method of reducing the density of the ethylene polymer is well known, rigidity (softens) lowered together so not preferred, for the purposes of thinning It is, for example, to a combination of two kinds of specific ethylene · alpha-olefin copolymer having a density, further, a three-component blend compositions plus certain HPLD in order to improve the moldability and transparency attempts to use have been made (for example, see Patent Document 4).
According to this method, excellent balance of conventionally impact strength and rigidity, although a polyethylene resin composition excellent in transparency is obtained, also decreases in impact strength due to HPLD blend is inevitable, further, three blend of ethylene polymer is considered economically disadvantageous than conventional in terms of stable supply of products constant quality at an industrial level.

On the other hand, as a method for improving the moldability, but attempts to introduce long-chain branching structure to increase the melt viscosity ethylene-based polymer have been made, inadequate optimization design of long chain branching structure Therefore, also decreases in strength and transparency can not be avoided, the improvement level was still insufficient (for example, see Patent documents 5-8).

Polyolefins prepared by olefin polymerization metallocene catalysts, highly uniform polymer molecular structure, such molecular weight distribution and the copolymer composition distribution, impact strength and long life, etc., since it is excellent in various mechanical properties, in recent years, their use the amount has been increasing. However, metallocene polyolefins, although excellent in mechanical various physical properties, because a narrow molecular weight distribution, is inferior in molding important properties of polyolefins such as melt tension and melt fluidity, a sufficient performance in the molding surface It did not satisfy.
As a method for improving the moldability of the poor metallocene polyolefins, to improve the flowability and melt tension by increasing the melt viscosity by introducing long chain branching in a polyethylene polymerization reaction using specific metallocene complexes the method is well known (e.g., see Patent Document 9.). The specific metallocene complexes of introducing long chain branching, crosslinking bisindenyl complexes (e.g., see Patent Documents 10-13.) And geometric constraint half metallocene complex (e.g., see Patent Document 14.) Well-known method using a It is but a long chain branch obtained by these methods, as the structure of HPLD is not developed, improvements in the melt viscosity of the polymer is not sufficient.

Further, as a method of long chain branching introduced metallocene complexes other than the above, a method for producing polyethylene containing long chain branches using bridged metallocene catalysts having a specific structure (for example, see Patent Document 15.) Is known is and, specifically, examples of using dimethylsilyl bis (pentadienyl) zirconium dichloride complex and diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride complex two metallocene complex simultaneously that are introduced, as the improvement technique, further, the two types of complexes were allowed to co-supported on the same carrier catalyst (e.g., see Patent documents 16-18.) and combined catalyst by improving the type of complex (for example, Patent Document 19, 20 references.) is known. These methods, one complex to form a polymer (so-called macromers) containing a polymerizable double bond at a terminal, other complex a complex excellent copolymerizability, copolymerizing the macromer it is said that forms a long-chain branched structure by.
However, even by these methods, the level although branched structure somewhat developed than a long chain branching structure of the conventional metallocene complex is introduced or a still insufficient, comonomer copolymerizable the two metallocene complex because large difference copolymer composition distribution of the produced polymer becomes wider, worsen the mechanical properties due to the formation of low-melting polymer has a problem that or cause.

Further, Patent Document 21, a cyclopentadienyl group and an indenyl group using an asymmetric metallocene and methylaluminoxane carbon bridge, when the homopolymerization of ethylene in solution polymerization, a polyethylene that can be produced with a branch Although There has been reported, the length of the branch is described as 1 to 20 carbon atoms, too short a length of the branches to express the effect of improving the moldability as long chain branching, distortion of elongational viscosity It does not show the cure.

Further, Patent Document 22, each the polymerization of propylene by a specific polymerization catalyst in combination with cyclopentadienyl groups and asymmetric metallocene compounds crosslinked indenyl group and methylaluminoxane having substituents have been reported, ethylene polymerization not according with long chain branching is generated when applied to, the effect of improving the moldability is not expected.

Furthermore, Patent Document 23, with a metallocene and a modified clay compound having a methyl group cyclopentadienyl group and an indenyl group at position 2,4,7 indenyl group of the asymmetric metallocenes silicon crosslinking, macromonomers as the catalyst system to produce useful ethylene polymers and ethylene / butene copolymer are reported, the polymer terminal double bonds is small, and there is no description of the long chain branching is generated with the catalyst alone.

Recently, the present inventors have, in Patent Document 24, of the asymmetric metallocene crosslinked cyclopentadienyl group and an indenyl group bridging group, no substituents other than the crosslinking groups on the cyclopentadienyl group, and has a hydrogen atom or a specific substituent on the indenyl group position 3, reported a method for producing a specific asymmetric metallocene essential components and the moldability by supported olefin polymerisation catalyst is improved ethylene polymer. According to the present invention, the strain hardening degree of extensional viscosity larger ethylene polymer are obtained, although the moldability of improvement over conventional long-chain branched polyethylene is observed, the branching index of long chain branching since still fall short of the high-pressure low-density polyethylene, the improvement of a further long chain branched structure has been demanded.

Under these circumstances, to solve the problems of conventional ethylene-based resin composition, molding processability is excellent, and polyethylene which can manufacture a molded article excellent in balance and transparency of impact strength and stiffness development of the resin composition has been desired. Furthermore, to solve the long-chain branch-containing polyethylene in the prior art, in order to improve the molding processability of metallocene polyethylene, ethylene-based polymer obtained by introducing long chain branching of sufficient number and appropriate length, the length chain branching introduced into the superior olefin polymerization catalyst, the development of a method for manufacturing the olefinic polymer has been desired.

Japanese Patent Laid-Open 7-149962 discloses Japanese Patent Laid-Open 9-31260 discloses Japanese Patent 2006-312753 JP Japanese Patent 2010-31270 JP International Publication No. WO 97/10295 Japanese Patent 2006-63325 JP Japanese Patent 2006-124567 JP Japanese Patent 2007-197722 JP Japanese Patent Laid-Open 2-276807 discloses Japanese Patent Laid-Open 8-48711 discloses Japanese Patent Laid-Open 8-311260 discloses Japanese Patent 2004-149760 JP Japanese Patent 2004-217924 JP Japanese Patent Laid-Open 6-306121 discloses Japanese Patent Laid-Open 7-252311 discloses Japanese Patent 2006-233208 JP Japanese Patent 2006-321991 JP Japan-T-2007-520597 Patent Publication No. Japan-T-2002-515521 Patent Publication No. Japanese Patent 2009-144148 JP Japanese Patent Laid-Open 5-043619 discloses Japanese Patent Laid-Open 7-224079 discloses Japanese Patent 2008-050278 JP Japanese Patent 2011-137146 JP

An object of the present invention has been made in view of the problems of the prior art described above, to provide an ethylene polymer moldability was improved. Further, another object of the present invention has been made in view of the problems of the prior art described above, excellent in molding properties, at the same time, excellent in balance between impact strength and rigidity, even polyethylene resin composition which is excellent in transparency providing an object, further, injection molding the polyethylene resin composition, compression injection molding, rotational molding, extrusion molding, blow molding, obtained by blow molding or inflation molding, balance of impact strength and stiffness and transparency and to provide a molded article excellent and molded article applications sexual. Furthermore, another object of the present invention, metallocene polyolefins, in particular for improving the molding processability of metallocene-based polyethylene, a sufficient number and appropriate length metallocene polyolefin or metallocene polyethylene has been introduced a long-chain branching and to provide an olefin polymerization catalyst component capable of producing olefin polymerization catalyst comprising the components, a process for producing an olefin polymer using the catalyst.
In the present invention, the polyethylene, ethylene homopolymers and means a generic name of a copolymer of ethylene and below the olefins, also translates into an ethylene polymer.

The present inventors have made intensive studies in order to achieve the above object, a specific ethylene-based polymer with less long chain branching structure characterized by extensional viscosity behavior, it is also characterized by extensional viscosity behavior specific the combination of a specific ethylene polymer having a long chain branching structure, was blended to both the specific MFR and density, polyethylene resin composition obtained is capable solve the above problems good It found to exhibit the characteristics, and have completed the present invention based on these findings.

That is, according to the first aspect of the present invention, ethylene polymer is provided that satisfies the following condition (B-1 ') ~ condition (B-6).
(B-1 ') MFR B = 0.001 ~ 200g / 10 minutes (B-2 ") Density B = 0.880 ~ 0.970g / cm 3
(B-3) [Mw / Mn] B = 2.0 ~ 10.0
(B-4 ') Temperature 170 ° C., elongation strain rate 2 extensional viscosity measured in (in 1 / sec) eta (t) (unit: Pa · sec) and elongation time t (in seconds) log-log plot of in the case where either inflection point of elongational viscosity due to strain hardening is not observed, or the inflection point is observed, the maximum elongation viscosity after strain hardening η B; Max (t 1) , before curing extension when a linear (t), η B; ; the approximate line viscosity eta B is linear (t 1) strain hardening degree which is defined by [λmax (2.0)] B; Max (t 1) / η B it is from 1.2 to 30.0.
(B-5) above condition (B-4 ') are defined in the same manner as in [λmax (2.0)] B and, when measured in the same manner elongation strain rate of 0.1 (in 1 / sec) of [λmax (0.1)] the ratio of B [λmax (2.0)] B /[λmax(0.1)] B is 1.2 to 10.0.
(B-6) is a polymer prepared by polymerization of ethylene using a catalyst containing a transition metal.

Further, according to the second aspect of the present invention, in a first aspect, further satisfying ethylene polymer of at least one of the following conditions (B-7) and condition (B-8) are provided that.
(B-7) differential refractometer, viscosity detectors, and branching index of the molecular weight of 1,000,000 determined by GPC measurement device combining a light scattering detector (g C ') is at 0.30 to 0.70 .
(B-8) differential refractometer, viscosity detectors, and the content of molecular weight of 1,000,000 or more components measured by GPC measurement device combining a light scattering detector (W C) is at 0.01 to 30% is there.

Further, according to the third aspect of the present invention, the ethylene polymer 41 to 99% by weight which satisfies (A) of the following conditions (A-1) ~ condition (A-4), (B) the first and a ethylene polymer 1-59 wt% according to the first or second invention and, MFR of the total composition is 0.05 ~ 50 g / 10 min, density of 0.910 ~ 0.960g / cm 3 polyethylene resin composition is provided at.
Conditions of the ethylene-based polymer (A);
(A-1) MFR A = 0.3 ~ 100g / 10 minutes (A-2) Density A = 0.915 ~ 0.970g / cm 3
(A-3) [Mw / Mn] A = 2.0 ~ 10.0
(A-4) Temperature 170 ° C., elongation strain rate 2 extensional viscosity measured in (in 1 / sec) eta (t) (unit: Pa · sec) and elongation time t: the log-log plot of (in seconds) If either inflection point of elongational viscosity due to strain hardening is not observed, or the inflection point is observed, the maximum elongation viscosity after strain hardening η a; Max (t 1) , extensional viscosity before curing when a linear (t), η a; ; approximate line of eta a of Max (t 1) / η a ; linear (t 1) strain hardening degree which is defined by [λmax (2.0)] a 1 it is 1.0 to 2.0.

Further, according to the fourth aspect of the present invention, the polyethylene resin in the third invention, the ethylene polymer (B) is, to satisfy the following condition (B-1) ~ condition (B-6) composition is provided.
Conditions of the ethylene-based polymer (B);
(B-1) MFR B = 0.01 ~ 1.5g / 10 min, and, 100> MFR A / MFR B > 1.0
(B-2) Density B = 0.880 ~ 0.940g / cm 3
(B-3) [Mw / Mn] B = 2.0 ~ 10.0
(B-4) is the third aspect of the invention is defined in the same manner as in conditions described (A-4) in [λmax (2.0)] B from 1.2 to 20.0 and 20> [λmax (2.0)] B /[λmax(2.0 )] a> 1.0.
(B-5) the third according to the invention conditions (A-4) and are defined in the same manner as [λmax (2.0)] B and, the elongation strain rate of 0.1 (in 1 / sec) when measured in the same manner as [λmax (0.1)] the ratio of B [λmax (2.0)] B /[λmax(0.1)] B is 1.2 to 10.0.
(B-6) is a polymer prepared by polymerization of ethylene using a catalyst containing a transition metal.

In addition, according to the fifth aspect of the present invention, in the third invention, the ethylene polymer (B) is a polyethylene based resin composition is provided that satisfies the further the following conditions (B-2 ') .
(B-2 ') 1.070> Density A / Density B> 0.990

The sixth aspect of the present invention, in the third invention, the ethylene polymer (A) is an ethylene by Ziegler-Natta catalyst produced using the magnesium compound and a titanium compound homopolymerization or polyethylene resin composition is an ethylene polymer or an ethylene · alpha-olefin copolymer produced by copolymerization of alpha-olefins is provided.

The seventh aspect of the present invention, injection molding polyethylene resin composition according to the third invention, compression injection molding, rotational molding, extrusion molding, obtained by blow-molding or blow-molding molded article It is provided.

The eighth aspect of the present invention, extrusion of the polyethylene resin composition of the third invention molding, blow molding, films obtained by blow molding or inflation molding is provided.

Further, according to the ninth aspect of the present invention, the catalyst components are provided for the polymerization of olefins comprising the following components (A-1b) and component (A-2b).
Component (A-1b): a metallocene compound represented by the following general formula (1b)

Figure JPOXMLDOC01-appb-C000006

Wherein (1b), M 1b represents any of the transition metals Ti, Zr or Hf. X 1b and X 2b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1b and Q 2b are each independently a carbon atom, a silicon atom or a germanium atom. R 1b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four at least two bonded out of R 1b, to form a ring together with Q 1b and Q 2b it may be. m b is 0 or 1, if m b is 0, Q 1b is directly bonded to the conjugated 5-membered ring containing R 2b and R 3b. R 2b, R 3b and R 4b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 2b, of R 3b and R 4b, or one pair of adjacent R 3b each other or adjacent R 2b and R 3b only may form a ring together with the carbon atom bonded. ]
Component (A-2b): a metallocene compound represented by the following general formula (2b)

Figure JPOXMLDOC01-appb-C000007

Wherein (2b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other. R 12b, R 14b and R 15b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, indicates an atom or group selected from halogen-containing hydrocarbon group, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom having 1 to 20 carbon atoms but of them, at least not one hydrogen atom. R 13b are each independently a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom. R 12b, R 13b, of R 14b and R 15b, between the adjacent R 12b, either one pair of adjacent R 13b together or adjacent R 12b and R 13b only, adjacent R 14b together, adjacent R 15b or between any one pair of adjacent R 14b and R 15b only, they may form a ring together with the bond to which carbon atoms. ]

Further, according to the tenth aspect of the present invention, the catalyst components are provided for the polymerization of olefins comprising a metallocene compound represented by the following general formula (1c).

Figure JPOXMLDOC01-appb-C000008

Wherein (1c), M 1c indicates one of the transition metals Ti, Zr or Hf. X 1c and X 2c are each independently hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1c and Q 2c are each independently a carbon atom, a silicon atom or a germanium atom. R 1c are each independently, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four to form a ring together with Q 1c and Q 2c and at least two members out of R 1c it may be. m c is 0 or 1, if m c is 0, Q 1c is directly bonded to the conjugated 5-membered ring containing R 2c. R 2c and R 4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1 to 6 having 1 to 20 carbon atoms, 1 to 4 carbon atoms halogen-containing hydrocarbon group of 1-20, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom. R 3c represents a substituted aryl group represented by the following general formula (1-ac). ]

Figure JPOXMLDOC01-appb-C000009
Wherein (1-ac), Y 1c is the periodic table group 14 shows a group 15 or 16 atom.R 5c, R 6c, R 7c , R 8c and R 9c each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, the number of carbon atoms containing a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen or nitrogen hydrocarbon group of 1 to 20, a hydrocarbon group-substituted amino group, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6 having 1 to 20 carbon atoms, carbon halogen-containing hydrocarbon group having 1 to 20, or a hydrocarbon group-substituted silyl group having a carbon number of 1 ~ 20, R 5c, R 6c, R 7c, R 8c and R 9c are joined adjacent groups , they may form a ring together with the bonded atoms to them. n c is 0 or 1, if n c is 0, there is no substituent R 5c to Y 1c. p c is 0 or 1, if p c is 0, carbon atoms carbon atoms and R 9c which R 7c is attached is bound is directly attached. If Y 1c is a carbon atom, R 5c, R 6c, R 7c, R 8c, at least one of R 9c is not a hydrogen atom. ]

The 11 th aspect of the present invention, olefin polymerization catalyst containing the olefin polymerization catalyst component of the ninth or tenth aspect is provided.

The 12 th aspect of the present invention, by using the olefin polymerization catalyst comprising the following components (A) and (B), among the conditions defined in the first aspect of the present invention, at least the conditions (B -4 ') the method of producing an ethylene polymer to produce an ethylene polymer which satisfies is provided a.
Component (A): The following catalyst component (A-i) ~ (A-iii) at least one of (A-i) the ninth olefin polymerization catalyst component of the invention (A-ii) the tenth a catalyst component for olefin polymerization of the invention (a-iii) olefin polymerization catalyst component comprising a metallocene compound represented by the following general formula (1d)

Figure JPOXMLDOC01-appb-C000010

Wherein (1d), M 1d represents any of the transition metals Ti, Zr or Hf. X 1d and X 2d are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1d and Q 2d are each independently a carbon atom, a silicon atom or a germanium atom. R 1d are each independently, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four to form a ring together with Q 1d and Q 2d and at least two members out of R 1d it may be. m d is 0 or 1, if m d is 0, Q 1d is directly bonded to the conjugated 5-membered ring containing R 2d and R 3d. R 2d and R 3d is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having silicon atoms 1-1 carbon atoms containing from 6 to 18 halogen containing 1 to 20 carbon atoms hydrocarbon group, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, not the least one hydrogen atom of R 2d. R 4d represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 5d is an atom or group bonded to the carbon atoms of R 4d, each independently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 1 containing silicon atoms 1-6 ~ 18 silicon-containing hydrocarbon group, a halogen-containing hydrocarbon group, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom having 1 to 20 carbon atoms. n d represents an integer of 0 to 10, if n d is 2 or more, at least two R 5d, together with binding to that carbon atom may form a ring. ]
Component (B): component reacts with the metallocene compound cationic metallocene compound to produce the (A).
Incidentally, in the twelfth aspect of the present invention, the olefin polymerization catalyst is particulate carrier (component (C)) may contain.

The 13 th aspect of the present invention, ethylene polymer of the first invention produced by the production method of the ethylene polymer of the twelfth aspect is provided.

In addition, according to the fourteenth aspect of the present invention, the polyethylene resin composition of the third invention using the first 13 ethylene polymer of the invention as the ethylene polymer is provided.

According to the present invention, it is possible to provide an ethylene polymer having excellent moldability which has a long-chain branched structure developed.
Further, the polyethylene resin composition of the present invention is excellent in molding properties, at the same time, excellent in balance between impact strength and rigidity, further has the effect of excellent in transparency, also said polyethylene resin composition injection molding, compression injection molding, rotational molding, extrusion molding, blow molding, molded product obtained by blow molding or inflation molding is also because an excellent balance of impact strength and stiffness and transparency, molding was thinned products it is possible to provide economic advantage to the.
Further, according to the present invention, to prepare an olefin polymerization catalyst component containing a specific metallocene compound, by using the same olefin polymerization catalyst, metallocene having long chain branching of sufficient number and appropriate length it is possible to provide a method of manufacturing a polyolefin or metallocene polyethylene. Then, it is possible to provide a method for improving the molding processability of metallocene-based polyethylene.

Figure 1 is a graph showing the baseline and interval of the chromatogram to be used in gel permeation chromatography (GPC). Figure 2 is a plot of extensional viscosity when the inflection point of the extensional viscosity is observed (a typical example of the ethylene polymer of Example (B)). Figure 3 is a plot of extensional viscosity when the inflection point of the extensional viscosity is not observed (a typical example of the ethylene polymer of Example (A)). 4 (a) is a molecular weight distribution curve calculated from GPC-VIS measurements (branch structure analysis), 4 (b) is a graph showing the relationship between the branching index (g ') and molecular weight (M).

The present invention is less specific ethylene-based polymers having long chain branching structure characterized by extensional viscosity behavior as (A), also specific ethylene-based polymer having a specific long-chain branched structure characterized by extensional viscosity behavior and (B), the polyethylene resin composition obtained by blending such a specific MFR and density, as well as those relating to the application of the molded body and the molded product obtained by molding the polyethylene resin composition is there. The present invention will now be described for each item.

Polyethylene resin composition polyethylene resin composition of the present invention [I] The present invention, certain conditions (A-1) ~ ethylene polymer satisfying the (A-4) (A) (hereinafter, simply ( also referred to as a) component.) 41 and to 99% by weight, ethylene polymer which satisfies the specific conditions (B-1) ~ (B-6) (B) (hereinafter, referred to simply as component (B).) and a 1-59 wt%, and, 0.05 ~ 50 g / 10 min MFR of the total composition, density, characterized in that a 0.910 ~ 0.960g / cm 3. Hereinafter, each component constituting the polyethylene resin composition of the present invention will be described the characteristics.

(1) ethylene polymer (A)
Polyethylene, one of the components constituting the resin composition (A) component of the present invention satisfies all of the conditions (A-1) ~ (A-4) described below.

1-1. Conditions (A-1)
A melt flow rate of component (A) in the present invention (MFR A) is, 0.3 ~ 100 g / 10 min, preferably 0.9 ~ 20 g / 10 min, more preferably 1.4 ~ 10 g / 10 min .
Moldability MFR A polyethylene based resin composition is less than 0.3 g / 10 min, particularly poor melt flowability and spreadability, MFR A is 100 g / 10 min larger than the polyethylene-based resin composition and molded article impact strength is not preferable because the mechanical strength such as tear strength and tensile strength decreases. In the present invention, ethylene polymer, the MFR of the polyethylene resin composition, the JIS K7210 - compliant "plastic test method for melt mass flow rate of thermoplastics (MFR) and melt volume flow rate (MVR)" to refer to the value of 190 ° C., as measured at 21.18 N (2.16 kg) load conditions.

1-2. Conditions (A-2)
Density A of the ethylene-based polymer (A) in the present invention, 0.915 ~ 0.970g / cm 3, preferably 0.917 ~ 0.950g / cm 3, more preferably 0.925 ~ 0.940 g / cm 3.
If the density A is in this range, balance and transparency of impact strength and rigidity of the polyethylene resin composition and molded article are excellent. On the other hand, the density A rigidity is reduced is less than 0.915 g / cm 3, if the product is a thin molded article having a thickness of a film or sheet or the like, various disadvantages in product use, of course, the product winding process, the surface it is not preferable because inconvenience in the process step after such printing and lamination, if the product is a thick molded article such as a pipe or various containers, for product is too soft deformation, the large thickness designed unnecessarily Sako It is not preferable because it is. Also, undesirable density A is 0.970 g / cm 3 greater than the impact strength and transparency is impaired. In the present invention, the density of the ethylene-based polymer, polyethylene-based resin composition refers to a value measured by the following method.

Pellets to create a pressed sheet 2mm thick by hot pressing, filled with distilled water placed in the sheet beaker 1000ml capacity, heated with a mantle heater was covered with a watch glass. After distilled water boiled for 60 minutes after boiling, allowed to cool The beaker was placed on a wooden base. Boiling distilled water after this time 60 minutes boiling is adjusted so as not time to less than 60 minutes to reach room temperature and 500 ml. Moreover, the test sheet is immersed in a substantially central portion of the water so as not to contact the beaker and the water surface. 23 ° C. The sheet, with 50% humidity conditions, after annealing at 24 hours 16 hours or more, the punching so that the vertical and horizontal 2 mm, at a test temperature 23 ° C., "plastic JIS K7112 - Density of non-foam plastic and in accordance with the measurement method "of specific gravity, it is measured.

1-3. Conditions (A-3)
The ratio of (A) of the present invention weight average molecular weight of the component (Mw) to number average molecular weight (Mn) ([Mw / Mn ] A) is 2.0 to 10.0, preferably 2.5 to 10.0 , more preferably 2.9 and 5.0. Moldability [Mw / Mn] polyethylene resin composition at A is less than 2.0, should be avoided in particular or poor melt flowability, there is a possibility of or hardly mixed with other polymer components.
[Mw / Mn] or A becomes the insufficient effect of greater than 10.0 and rigidity improvement of the polyethylene resin composition and molded article is not preferable because transparency is deteriorated. In the present invention, ethylene polymer, Mw and Mn of the polyethylene resin composition refers to a value measured by gel permeation chromatography (GPC).

Conversion from the holding capacitor to the molecular weight is carried out using a calibration curve with standard polystyrene prepared in advance. Standard polystyrene used are both less brand Tosoh Corp.. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
Each so that the 0.5 mg / mL, a solution prepared by dissolving ODCB (containing 0.5 mg / mL of BHT) and 0.2mL injected to create a calibration curve. The calibration curve used cubic obtained by approximation by the least square method. Viscosity equation used in conversion to molecular weight [η] = K × M α uses the following values.
PS: K = 1.38 × 10 -4 , α = 0.7
PE: K = 3.92 × 10 -4 , α = 0.733
PP: K = 1.03 × 10 -4 , α = 0.78

The measurement conditions of GPC are as follows.
Devices: Waters Corp. GPC (ALC / GPC 150C)
Detector: FOXBORO Co. MIRAN 1A IR detector (measurement wavelength: 3.42μm)
Column: Showa Denko Co., Ltd. AD806M / S (3 pieces)
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C.
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: samples using ODCB (containing 0.5 mg / mL of BHT), a solution of 1 mg / mL were prepared, dissolved over a period of about 1 hour at 140 ° C..
Incidentally, baseline and interval of the obtained chromatogram are carried out as illustrated in Figure 1.

1-4. Conditions (A-4)
(A) component in the present invention, the temperature 170 ° C., elongation viscosity measured at an elongation strain rate 2 (unit 1 / s) eta (t) (unit: Pa · sec) and elongation time t: the (in seconds) in a log-log plot, if either inflection point of elongational viscosity due to strain hardening is not observed, or the inflection point is observed, the maximum elongation viscosity η Max (t 1) after strain hardening, before curing when an approximate line of elongational viscosity was η linear (t), η Max (t 1) / η linear strain hardening degree which is defined by (t 1) [λmax (2.0 )] a is from 1.0 to 2 .0, preferably 1.0 to 1.5, more preferably from 1.0-1.2, most preferably, either if the inflection point is not observed, the [λmax (2.0)] a it is a case of from 1.0 to 1.1. The approximate line elongational viscosity before curing, where among the tangent of the curve of the log-log graph in the range of t corresponding to the strain amount 0.2 1.0, is that the most a small gradient tangent ( However, the inclined-out is a 0 or a positive value).
[Λmax (2.0)] A is the ethylene polymer is less than 1.0, or not a uniform molten state of the polyethylene resin composition and molded product, potentially thermally unstable structure There are, it is not preferable. Larger than [λmax (2.0)] A 2.0, although excellent in melt tension and fluidity during molding, or decreased the impact strength of the polyethylene resin composition and molded body, transparency worse undesirable or.

In general, polyethylene, film molding, blow molding, but is processed into industrial products by biasing type method via a molten state, such foam molding, extensional flow characteristics this time, as represented by the extensional viscosity and strain hardening degree but a significant impact on the ease of formability.
That is, a narrow molecular weight distribution, polyethylene having no long chain branching, because of the low melt strength is poor moldability, whereas a polyethylene having an ultra-high molecular weight component and long chain branching component, strain hardening (strain during melt extension hardening), i.e., extensional viscosity at high strain side has a sharp rising characteristics, polyethylene showing this characteristic significantly is excellent in moldability. Polyethylene resin having such elongation flow characteristics, for example, to prevent uneven thickness and breaking by blowing the products in film molding or blow molding, or enables high-speed molding, effect of high closed cell content during foam molding There is, the strength of the molded article improved design improvement, weight reduction, improvement of the molding cycle, but mean that the benefits of such thermal insulation improvement can be obtained, while, when 該伸 length flow characteristics too strong, at the time of molding or reduction occurs in the impact strength of the molded body by the intensity anisotropic molecular orientation is estimated to cause, like the worse the transparency by a decrease of the molded article surface smoothness characteristics melt elasticity is too strong it is estimated that the cause inconvenience occurs of.
Thus, to overcome disadvantages in mechanical properties surface improved and molding of the molding processed surface resulting elongation flow characteristics of polyethylene, devising a long-chain branched structure is a major controlling factors for 該伸 length viscosity properties result of intensive conducted studied polyethylene resin composition to solve by, as described above, less ethylene polymer having long chain branching structure (a) high MFR main component or low molecular weight side of the resin composition When used as a main component, the mechanical properties, particularly excellent in contribution to improvement of the rigidity, it was found that more excellent in transparency deterioration prevention.

Regarding the method of measuring the strain hardening degree, if measured uniaxial extensional viscosity, any method theoretically the same value can be obtained even in, for example, it is known document: Polymer 42 (2001) 8663 to the measuring method and instrument details are set forth.
Per the measurement of the ethylene-based polymer according to the present invention, a preferred measuring method and apparatus include the following.

Measuring method:
And equipment: Rheometorics manufactured by Ares
, Jigs: tea er Instruments Inc. Extentional Viscosity Fixture
Measurement temperature: 170 ℃
- strain rate: Creating 2 / sec · Test piece: Creating 18 mm × 10 mm by press molding, a thickness of 0.7 mm, the sheet.

Calculation method:
170 ° C., the elongation viscosity at a strain rate of 2 / sec, the horizontal axis represents time t (sec) is plotted extensional viscosity η a (Pa · sec) at logarithmic scale on the vertical axis. Its on a log-log graph, after strain hardening, and the maximum elongation viscosity of up to strain amount is 4.0 η Max (t 1) ( t 1 is the time when indicating the maximum extensional viscosity), before strain hardening when an approximate line of elongational viscosity was η linear (t), defines the value calculated as η Max (t 1) / η linear (t 1) strain hardening degree and (.lambda.max). Incidentally, the presence or absence of strain hardening, either has an inflection point changing from convex curve elongational viscosity above over time to downward convex curve, by whether, or not.
2 and 3 is a plot of a typical elongational viscosity. Figure 2 shows a case where the inflection point of the extensional viscosity is observed, η Max (t 1) in the figure, showing an η Linear (t). Figure 3 shows the case where the inflection point of the extensional viscosity is not observed.

1-5. (A) component in the composition the present invention of the ethylene-based polymer (A) is a copolymer of α- olefin homopolymers of ethylene or ethylene and 3 to 20 carbon atoms. As is α- olefin copolymer component used herein, propylene, butene-1,3-methylbutene-1,3-methylpentene-1, 4-methylpentene-1, pentene-1, hexene-1, heptene 1, octene-1, decene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1 and the like can be mentioned. These α- olefin may be only one kind, or may be used in combination more than two kinds. Among these, more preferred α- olefin are those having 3 to 10 carbon atoms, specifically propylene, butene-1,3-methylbutene-1,4-methylpentene-1, pentene-1, hexene-1 , heptene-1, octene-1, decene-1, and the like. Further preferred α- olefin are those having 4 to 8 carbon atoms, particularly butene-1,3-methylbutene-1,4-methylpentene-1, pentene-1, hexene-1, heptene-1, octene -1, and the like. Particularly preferred α- olefins are butene-1, hexene-1, octene-1. Incidentally, in the olefin polymerization catalyst described later, even when ethylene homopolymer, or without the α- olefins 1-butene and 1-hexene with ethylene oligomerization reaction in the polymerization system sub, "Chain called -walking reaction "active metal center in olefin polymerization growing end - and reacting the short-chain branching occurs, such a methyl group and an ethyl group are known from the isomerization reaction between the terminal carbon bound to the olefin polymer backbone, such short chain branching structure of the ethylene homopolymer of resulting from the reaction of may distinguish between short-chain branched structure resulting from the copolymerization of α- olefin is not attached.
Therefore, the ethylene homopolymer in the present invention means a resulting polymer polymerization is carried out without supplying alpha-olefin as comonomer externally, the ethylene · alpha-olefin copolymer, an external It refers to resulting polymer polymerization is performed by supplying the alpha-olefin from the word ethylene polymer ethylene homopolymer and an ethylene · alpha-olefin copolymer (comonomer other than below the alpha-olefin including.) collectively to use when used as.

Ratio of ethylene and alpha-olefin in the ethylene polymer is an ethylene about 80 to 100 wt%, from about 0-20% by weight alpha-olefin, preferably ethylene about 85 to 99.9 weight%, alpha- olefin is from about 0.1 to 15 wt%, more preferably ethylene about 90 to 99.5%, alpha-olefin is from about 0.5 to 10 wt%, more preferably ethylene about 90 to 99% by weight, α- olefin is about 1-10 wt%. Within ethylene content within this range, a good balance between rigidity and impact strength of the polyethylene resin composition and molded product is.

Copolymerization, alternating copolymerization, random copolymerization, no problem be any of block copolymer. Of course, it is also possible to use small amounts of comonomers other than ethylene and α- olefin, in this case, styrene, 4-methylstyrene, styrenes such as 4-dimethylamino styrene, 1,4-butadiene, 1,5 having hexadiene, 1,4-hexadiene, dienes such as 1,7-octadiene, norbornene, cyclic compounds cyclopentene such as hexenol, hexenoic acid, oxygen-containing compounds such methyl octene acid, a polymerizable double bond of equal mention may be made of the compound. However when using the dienes within a long chain branching structure is not developed, i.e. it goes without saying that should not not be used within a range satisfying the above conditions (A-4).

1-6. Component (A) in the process the present invention of the ethylene-based polymer (A) is used to produce the ethylene polymer of the composition that satisfies all the above conditions (A-1) ~ (A-4). Its production is carried out by a method for homo- or copolymerized with the above-mentioned α- olefins ethylene using an olefin polymerization catalyst.
The olefin polymerization catalyst, are known in various types today, whether the ethylene-based polymer (A) is capable prepared within the scope for improvement in structure and polymerization conditions and post conditions of the catalyst component without in any way being restricted so, suitable for the production of ethylene polymer (a), as a technique example for satisfying the economy in industrial level, a transition metal described in the following (i) ~ (iv) can examples of specific olefin polymerization catalyst comprising.

(I) Examples of suitable olefin polymerization catalysts in the production of Ziegler catalyzed ethylene polymer (A), Ziegler-Natta catalysts as the olefin coordination polymerization catalyst comprising a combination of alkyl compounds of transition metal compound and a typical metal and the like. Especially magnesium compounds called Mg-Ti system combines titanium compound as a solid catalyst component was supported organoaluminum compound to compound Ziegler catalysts (e.g., "catalyst utilization Encyclopedia; 2004 Kogyo Chosakai issued", "application system diagram - olefin Change of polymerization catalyst -;. which see 1995 invention Kyokai ", etc.) are preferable because of excellent high activity and polymerization process suitability inexpensive.
Among them, Japanese Sho 54-142192, JP-Japanese Sho 54-148093 Patent inert carrier such as described in Japanese substance-supporting Mg / Ti catalyst, i.e., for example, tetrahydrofuran anhydrous MgCl 2 TiCl 3 or a homogeneous mixture of TiCl 4, is previously impregnated in treated porous silica triethylaluminum catalyst and obtained solidified dry dry, described in Japanese Japanese JP 63-117019 and such catalyst obtained by subjecting an olefin prepolymerization Mg / Ti catalyst in the presence of an organic aluminum, for example, a solid component obtained by the reaction of MgCl 2 and Ti (OnBu) 4 and methylhydrodiene polysiloxane TiCl 4 and triethyl catalyst obtained by introducing a mixture of methylhydrodiene polysiloxane Aluminum presence, ethylene prepolymerized prepolymerized catalyst thus obtained, and the like. Further, a catalyst component containing a low-valent titanium atom obtained by reacting a magnesium aluminum complex and tetravalent titanium compounds as described in JP Japanese JP 60-195108 olefin polymerization catalyst is a combination of an organic aluminum compound, Japanese Sho 56-61406 Patent Publication magnesium ethoxide as described in, tri n- butoxy monochlorobenzene titanium, ethylaluminum homogeneous mixture of n- butanol sesquichloride obtained by dropping or the like solid catalyst, magnesium as described in Japanese Patent 2001-139635 Patent Publication, a halogen atom, an olefin polymerization solid catalyst comprising titanium and an electron donor, and the like and the like.

(Ii) the next generation Examples of suitable polymerization catalyst in the preparation of the metallocene catalyzed ethylene-based polymer (A), the metallocene catalyst (for example, "metallocene catalyst is an olefin polymerization catalyst comprising a metallocene-type transition metal compound and a cocatalyst component polymer industry technology (top-MZ); see 1994 inter research Corporation issued ", etc.) are relatively inexpensive excellent high activity and polymerization process suitability, even the molecular weight distribution and the copolymer composition distribution is narrow It is used because the ethylene polymer is obtained.
Of these, Japan catalyst system and for the polymerization of olefins comprising the alumoxane and a so-called metallocene complexes as described in JP 60-35007 Patent Publication, Japanese Patent No. 8-34809, JP-Japan JP-8-127613 and JP Japanese Hei 11-193306 discloses, Japanese Kohyo 2002-515522 discloses, by the co-catalyst component other than an alumoxane, such as catalyst system suitably used according to an equal used. Ti The metallocene complex center metal is periodic table Group 4B, Zr, those of Hf is preferably used exhibits a high activity against ethylene polymerization. The structure of the ligand of these metal center is known as the current of various structures, molecular weight of the polyethylene, the polymerization performance such as α- olefin copolymerizable being examined. Ethylene polymer (A) of the present invention is suitably intended to contain only a small amount or a long-chain branched structure is not as described above, the production of the ethylene polymer of such properties, the conjugated five-membered preferably the ring structure ligand is a so-called non-crosslinked complexes are not cross-linked by a cross-linking group with other ligands, for example, as in Japanese Unexamined Japanese Patent Application Laid-Open No. 11-310612, the general formula [ 1], represented by [2], [3] or [according to the structure classification of the metallocene compound according to 4] is preferably a compound represented by the general formula [1] or general formula [3], the general formula [1] compounds are more preferable. However, the generation of the long-chain branched structure the higher the concentration in the polymerization system of ethylene and α- olefin, since the polymerization reaction time is more are said to be disadvantageous short, the magnitude of the suitability of the metallocene compound merely polymerization There is the of course limited to the assumed relative things when implemented in the same conditions. Further, Japanese Patent Laid-Open 5-132518 and JP Japanese Patent 2000-154196 discloses metallocene complexes described in Japanese Patent 2004-161760 Patent Laid are preferably used, also, for example, Japanese metallocene complex having a monocyclic or polycyclic heteroaromatic group containing a heteroatom Kohyo 2002-535339 JP as a substituent on a conjugated five-membered ring structure ligand also preferably used.

Figure JPOXMLDOC01-appb-C000011

[Wherein, A 1 ~ A 4 is a ligand having a conjugated five-membered ring structure (A 1 ~ A 4 in the same compound may be the same or different), Q 1 is two conjugated five-membered a binding group which crosslinks the cyclic ligands at an optional position, Z 1 and Z 2 comprise each independently a nitrogen atom which is bound to M, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom ligand, a hydrogen atom, a halogen atom or a hydrocarbon group, a bonding group Q 2 is bridging the arbitrary position and Z 2 conjugated five-membered ring ligand, M is selected from group 4 of the periodic table a metal atom, and X and Y are each independently a hydrogen atom bound to M, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, respectively . More detailed definition shall comply with publication. ]

(Iii) Phillips catalyst Phillips catalyst, silica chromium compound, silica - alumina, silica - is supported on an inorganic oxide support such as titania, by activation in a non-reducing atmosphere, at least a portion of the supported chromium elements which is a chromium catalyst the chromium element was hexavalent (for example, M.P.McDaniel al., Advances in Catalysis, Volime 33,47 pp., 1985, Academic Press Inc .; M.P.McDaniel al., Handbook of Heterogeneous Catalysis, 2400 pages, 1997, VCH; M.B.Welch et al., Handbook of Polyolefins: Synthesis and Properties, 21 pp., 1993, See arcel Dekker, etc..). Phillips catalysts are preferably used exhibits a high activity against ethylene polymerization. However, the ethylene-based polymers produced by Phillips catalysts or contain long-chain branched structure, because the molecular weight distribution is broad tendency, ethylene polymer (A) when used as the above-mentioned conditions of the present invention ( a-3) and in particular should be noted that satisfy the (a-4).

Examples of suitable polymerization catalysts for the preparation of (iv) post-metallocene catalyzed ethylene-based polymer (A), is an olefin polymerization catalyst using a homogeneous metal complex other than a metallocene-based transition metal compound of the foregoing (nonmetallocene complex) post-metallocene catalyst (for example, "polyethylene technology readings; 2001 industry Committee (Ltd.) issued", "living polymerization by homogeneous transition metal catalyst; 1999 IPC Co., Ltd. issued", "catalyst utilization Encyclopedia; 2004 see Kogyo Chosakai issue ", and the like.) is excellent in relatively inexpensive activity is used since the more the molecular weight distribution and the copolymer composition distribution is narrow ethylene polymer is obtained.
Among them, Japanese Kohyo 10-513489 and JP Japanese Kohyo 2002-521538 discloses, Japanese Kohyo 2000-516295 discloses, Japanese Kohyo 2000-514132 discloses, Macromolecules, 1996, p5241, JACS , 1997,119, p3830, JACS, 1999,121, p5798, Organometallics, 1998, periodic table 3 ligand having at least two N atoms as disclosed in p3155 and the like through the two N atoms wherein bisimide compound of a transition metal having a four to eight membered ring chelate structure containing the transition metal, which is formed by binding to ~ 11 group transition metal, Iminoamido compounds and bisamide compound and, Japanese Patent No. 6-136048 discloses When less is disclosed in equal Four ligands having two O atoms or S atoms comprising the transition metal, which is formed by combining a transition metal of Group 3 to 11 of the periodic table via two O atoms or S atoms the - bis hydrocarbyloxy compound of a transition metal having an eight-membered ring chelate structure and bis hydrocarbylthio compounds and, Japanese Kohyo 2000-514132 discloses, Japanese Kohyo 2003-535107 discloses, Japanese Patent 2007-77395 JP at least one N atom are disclosed in equal, S atom or P atom and ligand the N atom having a carboxyl group (COO), the periodic table through S atom or P atom and a carboxyl group 3-11 Iminokarubokishi transition metal having a four to eight membered ring chelate structure containing the transition metal, which is formed by binding to group transition metals Over preparative compounds, thiocarboxylate compounds and phosphine carboxylate compound and a ligand having at least one P atom or N atom and the carbonyl group as disclosed in Japanese Kohyo 2004-517933 Patent Publication (CO) β- keto transition metal but having a four to eight membered ring chelate structure containing the transition metal, which is formed by binding to the 3 to 11 group transition metal in the periodic table via the P atom or N atom and the carbonyl group - phosphine compounds, beta-keto - imide compounds and beta-keto - amide compounds and, Japanese Sho 64-14217 discloses at least one P disclosed in Japanese Kohyo 2004-517933 Patent Publication transition atom or ligand having a N atom and O atom of the group 3 to 11 of the periodic table through the P atoms or N atoms and O atoms Phosphine compounds, .gamma.-oxy - - .gamma.-oxy transition metal having a four to eight membered ring chelate structure containing the transition metal, which is formed by combining the metal imide compound and .gamma.-oxy - and amide compounds, Japan JP-6-184214 and JP Japanese Hei 10-195090 discloses, Japanese Kohyo 2002-521534 discloses, Japanese Patent 2007-46032, JP-disclosed Japanese Patent 2007-77395 Patent Laid formed by ligand binding to the transition metal of group 3 to 11 of the periodic table through the P atoms and a sulfonic acid residue having at least one P atom and a sulfonic acid residue (SO 3) being is the transition metal having a four to eight membered ring chelate structure including the transition metal γ- sulfonato - phosphine compound and, Japanese Patent No. 11-315109 discloses , Chemical Communications (2003), (18), 3 to Group 11 of the periodic table through O atom of the ligand is the N atom and a phenoxy group having at least N atom and a phenoxy group as disclosed 2272-2273 etc. phenoxyimine compounds and phenoxy amine compounds of transition metals having a four to eight membered ring chelate structure containing the transition metal, which is formed by combining a transition metal is preferably used.
These non-metallocene complex catalyst, Ti central metal is periodic table Group 4B, Zr, Hf or V, Cr, Fe, Co, Ni, those Pd is more preferably used exhibits a high activity, central metal Ti, Zr, Hf, Fe, Ni, those Pd is further preferably used. However, some of these post metallocene catalysts, or contains long chain branched structure in the product ethylene polymer, or contains a short-chain branched structure around the methyl branches, they tend to spread or molecular weight distribution because it may have, when used as the ethylene polymer (a) of the present invention are particularly should be noted that satisfies the above conditions (a-2) ~ (a-4).

In the present invention, the production of ethylene polymer (A) is preferably the above olefin polymerization catalyst (i) ~ (iv), more preferably in contact with the ethylene (i) a Ziegler catalyst or (ii) a metallocene catalyst It is carried out by polymerizing or copolymerizing ethylene. Olefin polymerization catalysts may be used a plurality of types among (i) ~ (iv). In performing the polymerization or copolymerization of ethylene, slurry polymerization, solution polymerization, bulk polymerization in the liquid monomer in, such as a liquid phase polymerization method or a gas phase polymerization method such as suspension polymerization, it is adopted any method it can. For slurry polymerization method, slurry polymerization method using a pipe loop reactor, a slurry polymerization method using an autoclave type reactor, all of which can be used. With respect to the industrial polymerization process, Kazuo Matsuura Naotaka Mikami ed., "Polyethylene technology Reader", 148 pages, 2001, are described in detail in the Industrial Committee. Preferably slurry polymerization or gas phase polymerization as a polymerization method, gas phase polymerization is more preferable.

Ethylene used in the present invention may be an ethylene produced from crude oil from conventional fossil materials may be an ethylene plant-derived. Moreover, polyethylene produced in the present invention, no problem even in the ethylene polymer produced using ethylene plant-derived. The ethylene and polyethylene plant origin, for example, ethylene and the polymer described in JP Japanese Kohyo No. 2010-511634. Ethylene and the polymer of plant origin has the property of carbon neutral (not lead to an increase in carbon dioxide in the atmosphere without using fossil materials), it is possible to provide environmentally friendly products.

Liquid phase polymerization is carried out in the normal hydrocarbon solvent. The hydrocarbon solvents, propane, n- butane, isobutane, n- pentane, isopentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, alone or in mixtures or liquid monomer inert hydrocarbon such as xylene using It is. Gas phase polymerization process, under an inert gas coexists, fluidized bed, can adopt a normal polymerization method known in the stirred bed or the like, optionally coexist medium polymerization heat removal, it is also possible to employ a so-called condensing mode .

The polymerization temperature is generally from 0 ~ 300 ° C., is practically a 50 ~ 270 ° C., more preferably, varies depending employed to polymerization process, at 60 ~ 110 ° C. In a slurry polymerization or suspension polymerization There, the bulk polymerization in solution polymerization and liquid ethylene in a 100 ~ 250 ° C., in the gas phase polymerization is 60 ~ 100 ° C.. Catalyst concentration and olefin concentration in the reactor can be any concentration sufficient to proceed polymerization. Ethylene concentration, slurry polymerization, suspension polymerization, in the case of solution polymerization, can be from about 1% to about 10% of the range based on the weight of the reactor contents, the case of gas phase polymerization, as the total pressure it can be in the range of 0.1 ~ 10MPa. It is also possible to carry out the polymerization coexist hydrogen, it is common as a means for adjusting the MFR of the ethylene-based polymer (A). Hydrogen is generally has a function as a so-called chain transfer agent to control molecular weight. MFR is the polymerization temperature, by varying the polymerization conditions the molar ratio or the like of the catalyst can be somewhat adjusted. To reduce the long chain branching of the ethylene-based polymer (A), the ethylene concentration and the hydrogen concentration is preferably higher.

As the polymerization method, the reactor not only the single-stage polymerization for producing an olefin polymer using one, at least to improve the production, or molecular weight distribution or comonomer composition distribution in order to more precisely control two One or more reactors in series or / and ligated in parallel can be performed multi-stage polymerization. For multi-stage polymerization, by connecting a plurality of reactors, series multi-stage polymerization is preferably supplied by subsequently resulting reaction mixture was polymerized continuously in the second stage and subsequent reactors in the reactor of the first stage. The serial multi-stage polymerization method, the polymerization reaction mixture at the preceding stage of the reactor is transferred by continuously discharged through connecting pipe to subsequent secondary reaction vessel. Further, in the polymerization system, component intended for water removal can be carried out without any trouble be added a so-called scavenger. Such scavengers include trimethyl aluminum, triethyl aluminum, organoaluminum compounds such as triisobutylaluminum, the organoaluminum oxy-compound, an organic zinc compound, an organic magnesium compound is used, the organoaluminum compound is most common.

(2) the ethylene polymer (B)
One of components constituting the polyethylene resin composition is the component (B) of the present invention satisfies all of the conditions (B-1) ~ (B-6) to be described below.

2-1. Conditions (B-1)
In the present invention component (B) has a melt flow rate (MFR B) is, 0.01 ~ 1.5 g / 10 min, preferably 0.05 ~ 1.0 g / 10 min, more preferably from 0.1 to zero. is 8g / 10 minutes.
Moldability MFR B is polyethylene resin composition is less than 0.01 g / 10 min, particularly poor melt flowability and spreadability, to further becomes difficult to mix uniformly with the ethylene polymer (A) undesirable, gels, fish eyes, appearance defect or caused such fish eye, since the impact strength and transparency is lowered. MFR B is undesirably 1.5 g / 10 min impact strength larger than the polyethylene-based resin composition and molded body, mechanical strength and transparency improving effect of such tear strength and tensile strength is not sufficiently exhibited. MFR B Furthermore, in relation to the MFR A, 100> MFR A / MFR B> 1.0 the polyethylene resin composition and impact strength of the molded body that is the present invention to satisfy, tear strength and tensile strength, etc. mechanical strength, it is necessary to improve the transparency, preferably 20> MFR a / MFR B> 1.1, more preferably 15> MFR a / MFR B> 1.2, more preferably 10> MFR a / it is necessary to satisfy the MFR B> 2.0. Incidentally, MFR B is a value when measured under the same conditions as the above conditions (A-1).

2-2. Conditions (B-2)
Density B of the component (B) in the present invention, 0.880 ~ 0.940g / cm 3, preferably 0.891 ~ 0.940g / cm 3, more preferably 0.895 ~ 0.925g / cm 3, more preferably 0.900 ~ 0.915g / cm 3, particularly preferably 0.900 ~ 0.910g / cm 3.
If the density B is in this range, balance and transparency of impact strength and rigidity of the polyethylene resin composition and molded article are excellent. On the other hand, the density B rigidity is lowered is less than 0.880 g / cm 3, if the product is a thin molded article having a thickness of a film or sheet or the like, various disadvantages in product use, of course, the product winding process, the surface it is not preferable because inconvenience in the process step after such printing and lamination, if the product is a thick molded article such as a pipe or various containers, for product is too soft deformation, the large thickness designed unnecessarily Sako It is not preferable because it is. Also, or tackiness becomes badly difficult to handle even at room temperature when subjected to blending process of ethylene polymer (A), not preferable causing product stickiness of the polyethylene resin composition, and more , it reduces the compatibility with the ethylene polymer (a), the phase impact strength and transparency by the separation is likely to deteriorate. Also, undesirable density B 0.940 g / cm 3 greater than the impact strength and transparency is impaired.

Furthermore density B, in relation to the density A, 1.070> polyethylene resin composition and impact strength of the molded article of density A / density B> 0.990 present invention to meet the tear strength and tensile strength mechanical strength etc., preferably in the improvement of transparency, more preferably 1.059> density a / density B> 1.000, more preferably 1.050> density a / density B> 1.005, particularly preferably it is required to meet 1.035> density a / density B> 1.010. The density B is a value when measured under the same conditions as the above conditions (A-2).

2-3. Conditions (B-3)
The ratio of (B) in the present invention the weight average molecular weight of the component (Mw) to number average molecular weight (Mn) ([Mw / Mn ] B) is 2.0 to 10.0, preferably 2.0-6.0 , more preferably from 2.5 to 5.6 and more preferably 2.9 to 4.5, and particularly preferably 3.2 to 4.0.
[Mw / Mn] B is less than 2.0 should be avoided because it may or hardly mixed with the ethylene polymer (A). [Mw / Mn] or B becomes insufficient, the effect of the impact strength improvement of greater than 10.0 and a polyethylene resin composition and molded article, deteriorated transparency, undesirably tends to stickiness. Incidentally, it refers to a value when measured under the same conditions as [Mw / Mn] B is the above conditions (A-3).

2-4. Conditions (B-4)
(B) component in the present invention, the strain hardening degree [λmax (2.0)] B from 1.2 to 20.0 preferably 1.2 to 10.0, more preferably from 1.7 to 8.0 , more preferably from 2.4 to 6.0, and particularly preferably 3.0 to 5.0.
[Λmax (2.0)] B is the ethylene polymer is less than 1.2, the fluidity and the melt tension of the polyethylene resin composition and the molded product is insufficient, the molding processability is deteriorated. And [λmax (2.0)] B is greater than 20.0, although excellent in flowability and melt tension, lowered impact strength of the polyethylene resin composition and molded article, transparency deteriorates undesirably. Incidentally, it refers to a value when measured under the same conditions as [λmax (2.0)] B is the above conditions (A-4). Furthermore, [λmax (2.0)] relationship B and [λmax (2.0)] B, the ratio is, 20> [λmax (2.0) ] B /[λmax(2.0)] B > if it meets 1.0, preferably than the balance of the moldability and mechanical properties of the polyethylene resin composition of the present invention is particularly improved. If the ratio is more than 20, although the moldability of the resin composition will be improved, lowered mechanical strength, deteriorates transparency, ethylene polymer (A) and the ethylene polymer (B since uniform mixing of) the may exacerbate the appearance becomes difficult, undesirably. In the case the ratio is 1.0 or less, since the moldability improvement of the resin composition is not sufficiently exhibited, which is not preferable. Ratio is preferably 10> [λmax (2.0)] B /[λmax(2.0)] B> 1.1, more preferably 5.0> [λmax (2.0)] B / [λmax (2.0)] B> 1.5, more preferably 4.0> [λmax (2.0)] B /[λmax(2.0)] B> 1.8.
For the effect of extensional flow properties of the polyethylene it has on the mechanical properties surface of the molding processability and the molded body, is already as described in general terms in the section above conditions (A-4). Thus to overcome disadvantages in mechanical properties surface improved and molding of the molding processed surface resulting elongation flow characteristics of polyethylene, by devising a long-chain branched structure is a major controlling factors for 該伸 length viscosity properties in result of intensive conducted studied polyethylene resin composition in order to solve, with use fewer ethylene polymer having long chain branching structure (a) as a high MFR main component or low molecular weight side the main component of the resin composition , conditions defined extended strain hardening degree (B-4) [λmax ( 2.0)] lower MFR main more ethylene polymers having long chain branching structure is representative of (B) of the resin composition B When used as a component or high molecular weight side the main component, of course the improvement of molding properties, mechanical properties, particularly excellent in rigidity and impact strength, it was found that more excellent in transparency. Furthermore, when having a characteristic of long chain branching structure of the ethylene polymer (B) is the strain rate dependence of the elongation strain hardening degree is represented by the different following conditions (B-5) from the one previously used , molding properties of the polyethylene resin composition, mechanical properties, be very excellent improvement effect in any of transparency was found.

2-5. Conditions (B-5)
(B) component in the present invention, a defined above condition (B-4) [λmax ( 2.0)] B, which is measured as elongation strain rate of 0.1 (in 1 / sec) [λmax (0.1)] ratio of B [λmax (2.0)] B /[λmax(0.1)] B from 1.2 to 10.0, preferably 1.3 to 5.0 more preferably 1.4 to 4.0, more preferably 1.5 to 3.0.
[Λmax (2.0)] B /[λmax(0.1 )] B is the ethylene polymer is less than 1.2, or not a uniform molten state of the polyethylene resin composition and molded product, thermal or there could be a labile structure, very long long chain present in deterioration of reduction and transparency of the impact strength according to the strength anisotropy of the molded body due branched structure is or generated, preferably Absent.[Λmax (2.0)] B /[λmax(0.1 )] B is larger than 10.0, although excellent in melt tension and fluidity during molding, the polyethylene resin composition and molded article of the or impact strength decreases, unfavorably the transparency is deteriorated.

2-6. Conditions (B-6)
(B) component in the present invention is a polymer prepared by polymerization of ethylene using a catalyst containing a transition metal, preferably below 2-10. Ethylene polymer (B) of claim or [V] ethylene polymer of the claim in the production by the polymerization reaction of ethylene using a catalyst comprising the described transition metal details of the manufacturing method the heavy of the present invention the process a coalescing, and more preferably, a polymer prepared by coordination anionic polymerization reaction of ethylene using a catalyst containing a transition metal.
Today, as the ethylene polymerization catalyst containing no transition metals are known various radical polymerization initiator well, specifically dialkyl peroxides compounds, alkyl hydroperoxides compounds, benzoyl peroxide, such as hydrogen peroxide things, azobisisobutyronitrile, azo compounds such as azo-bis-cyclohexane carbonitrile, but and the like, the ethylene polymer produced in the radical polymerization reaction using these radical polymerization initiators, a long chain branched structure contains a large amount, when used as a component of the polyethylene resin composition, but have an effect on improvement of molding properties and transparency, since too many long chain branched structure decreases the strength of the composition and molded article not preferred, also, or sufficiently low MFR of the ethylene-based polymer (B), or sufficient to reduce the density, good Since copolymerization of Shii α- olefin or a unfeasible, because it is impossible to sufficiently improve the strength of the composition and molded article, which is not preferable. Incidentally, even if a catalyst comprising a transition metal, when the polymerization reaction as a so-called redox systems such as hydrogen peroxide / ferrous chloride or cerium salt / alcohol proceeds in a substantially radical polymerization, not regarded as a catalyst comprising a transition metal in the present invention.

2-7. Conditions (B-7)
(B) component in the present invention, in addition to the above condition (B-1) ~ (B-6), differential refractometer, viscosity detectors, and is measured by GPC measurement device combining a light scattering detector that branching index in the molecular weight of 1,000,000 (g C ') is preferably a .30 to .70. g C 'value is more preferably 0.30 to 0.59 more preferably 0.35 to 0.55, and particularly preferably 0.35-0.50. g C 'value is not preferable 0.70 larger than or insufficient moldability of the polyethylene resin composition, the transparency of the resin composition and molded product is or insufficient. g and C 'value of 0.30 less than the moldability of the polyethylene resin composition is improved, lowered impact strength of the molded body is not preferable because transparency is deteriorated. In the present invention, g C of the ethylene-based polymer 'W C value of values and the following paragraph, the molecular weight distribution curve or the branching index calculated from the GPC-VIS measurements following (g' long chain branching of using) it is an evaluation technique.

2-8. Conditions (B-8)
(B) component in the present invention, in addition to the above condition (B-1) ~ (B-7), differential refractometer, viscosity detectors, and is measured by GPC measurement device combining a light scattering detector that the content of molecular weight of 1,000,000 or more components (W C) is preferably from 0.01 to 30.0 percent. W C value is more preferably 0.01 to 10.0%, more preferably from 0.02 to 8.0%, particularly preferably 0.05 to 6.0% and most preferably is 0.09 to 4.0 percent.
W C value undesirable or insufficient moldability 0.01% smaller than the polyethylene-based resin composition, the transparency of the resin composition and molded product is or insufficient. W and C value is greater than 30.0%, of the molding processability of the polyethylene resin composition, the melt tension is improved, too low melt flowability, manufacturing and molding of the resin composition it is not preferable because hindered, even lowered impact strength of the molded body is not preferable because transparency is deteriorated.

[Branched structure by GPC-VIS analysis]
As GPC apparatus equipped differential refractometer (RI) and Viscosity detector (Viscometer), using a Waters Corporation Alliance GPCV 2000. Further, as the light scattering detector, using a multi-angle laser light scattering detector (MALLS) Wyatt Technology Inc. DAWN-E. Detector was connected MALLS, RI, in the order of Viscometer. Mobile phase solvent is 1,2,4-trichlorobenzene (an antioxidant Irganox1076 at a concentration of 0.5 mg / mL). Flow rate is 1mL / min. Column was used in conjunction two Tosoh Corporation GMHHR-H (S) HT. The temperature of the column, the sample injection section and each detector is 140 ° C.. Sample concentration was 1 mg / mL. Injection volume (sample loop volume) is 0.2175ML. Absolute molecular weight obtained from MALLS (M), the inertial square radius (Rg) and intrinsic viscosity derived from Viscometer In obtaining the ([eta]) may utilize MALLS supplied data processing software ASTRA (version4.73.04) , it was calculated by the following literature reference.

References:
1. Developments in polymer characterization, vol. 4. Essex: Applied Science; 1984. Chapter1.
2. Polymer, 45, 6495-6505 (2004)
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

[Branching index (g C ') calculated such]
The branching index (g ') is calculated, the intrinsic viscosity obtained sample was measured by the above Viscometer (ηbranch), separately, as the ratio of the intrinsic viscosity obtained by measuring the linear polymer (ηlin) (ηbranch / ηlin) to.
When long chain branches are introduced into the polymer molecule, the radius of gyration becomes smaller as compared with the linear polymer molecules of the same molecular weight. Since the intrinsic viscosity when the inertia radius, the smaller the ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of the linear polymer of the same molecular weight in accordance with the long-chain branches are introduced (ηlin) (ηbranch) (ηbranch / ηlin) is small made to go. Therefore, when branching index (g '= ηbranch / ηlin) becomes a value smaller than 1 means that the branch is introduced, long chain branches are introduced is gradually increased in accordance with its value decreases it means that. In particular, in the present invention, as the absolute molecular weight obtained from the MALLS, the molecular weight of 1,000,000 or more components, the content ratio (%) to the total amount of components measured in RI, the content of molecular weight of 1,000,000 or more components (W C) calculated as, as an absolute molecular weight obtained from the MALLS, 'a, g C' above g in molecular weight of 1,000,000 is calculated as.
Shows an example of the analysis result by the GPC-VIS in FIGS. 4 (a) and 4 (b). 4 (a) is a molecular weight obtained from MALLS a (M) and measured on the basis of the concentration obtained from the RI molecular weight distribution curve, Fig. 4 (b), branching index in the molecular weight (M) (g ') a representative. Here, as the linear polymer, with linear polyethylene Standard Reference Material 1475a (National Institute of Standards & Technology).

2-9. Description of the composition of the component (B) in the composition the present invention of the ethylene-based polymer (B), except the ratio of ethylene and α- olefin, the above-mentioned 1-5. Since the ethylene polymer explanation of the composition of (A) can be referred to as, with respect to same portions will not be described.
Ethylene polymer (B) of the present invention, preferably, ethylene and the above-mentioned 1-5. A copolymer of the α- olefin described, most preferably, hexene-1, a copolymer of octene-1. Ratio of ethylene and the alpha-olefin in the ethylene-based polymer (B) of the present invention, ethylene about 75 to 99.5 wt%, alpha-olefin is from about 0.5 to 25 wt%, preferably from about ethylene 78-97% by weight, from about 3 to 22% by weight alpha-olefin, more preferably ethylene about 80 to 96 weight%, alpha-olefin is about 4-20 wt%, more preferably ethylene about 82 to 95 weight %, about 5 to 18 weight% alpha-olefin. Within ethylene content within this range, the balance between rigidity and impact strength of the polyethylene resin composition and molded body is good, excellent in transparency. When using the above dienes of course it should not not be used within a range satisfying a long-chain branched structure above condition (B-4) and (B-5).

2-10. Ethylene polymer ethylene polymer in the preparation method the present invention (B) described relates to a process for the preparation of (B), the above condition (B-4) and the ethylene-based to long chain branched structures corresponding to (B-5) Weight except that it is necessary to pay attention to the selection of appropriate olefin polymerization catalyst to impart to the polymer (B), the above-mentioned 1-6. Since the ethylene-based polymer process regarding the description of (A) can be referred to as, with respect to same portions will not be described.
Suitable for the production of ethylene polymer in the present invention (B), an olefin polymerization catalyst comprising a transition metal to satisfy the economy in industrial level, as in the case of the ethylene polymer (A), the aforementioned ( i) a Ziegler catalyst, (ii) a metallocene catalyst is suitably selected from (iii) Phillips catalyst, or (iv) post-metallocene catalysts.
Suitable the catalyzed production of ethylene polymer (B) in the present invention, (i) a Ziegler catalyst, (ii) a metallocene catalyst, (iv) a post metallocene catalyst, even more preferably (i) a Ziegler catalyst, (ii) a metallocene catalyst. Among them (ii) a metallocene catalyst, as compared to other catalysts, since the molecular weight distribution and a copolymer composition distribution to generate a narrow ethylene polymer, the mechanical properties of the polyethylene resin composition and molded article, transparent sex, tackiness preventing performance, in terms of improvement of such heat-sealing performance, is particularly suitable. Of course, (iv) even in the post metallocene catalysts, their use is preferred of course in the case of selecting a catalyst that exhibits comparable performance in the metallocene catalyst and this point of view.

Of satisfaction to be characteristic of the ethylene-based polymer (B) in the present invention, particularly important to become the condition (B-4) and condition (B-5), preferably conditions (B-4), condition (B- 5), and condition (characteristic represented by B-7), the degree which can be entangled with each other at the level of elongation strain hardening behavior is observed, the corresponding amount containing well developed short or eye branched structure interpretation believed to be derived from the characteristic long chain branched structure is.

The generally ethylene polymer having long chain branching, an ethylene polymer having a long branched structures polyethylene molecules (long chain branching), ethylene homopolymer and ethylene having short chain branching customary α- olefin copolymer is contrasted with (also referred to linear polyethylene). Method for producing ethylene polymer, so far have also been various attempts to copolymerize directly with ethylene and α-olefins using a recent Ziegler catalyst or a metallocene catalyst having such long chain branching , or a method of ethylene and allowed advance to the manufactured macromonomer co polymers and to introduce long chain branching and the like. Moreover, it is said that the ethylene polymer by the catalyst, of which central metal is hexavalent chromium elements called Phillips catalyst contains a small amount of long chain branching structure. As the example described the preparation of ethylene polymer having a specific long-chain branched structure, for example, recently, the Japanese Sho 60-090203 JP and Japanese Patent as those using a Ziegler type catalyst No. 10-298234 discloses the like. In these methods, and the type and amount of the organic aluminum compound, by controlling the quality and quantity of properly selected and long chain branching the catalyst type and polymerization conditions, the long-chain branched structure of the ethylene-based polymer it is possible to adjust. Further, as those using a metallocene catalyst, as an example of using the complex having a bridged bis cyclopentadienyl ligand, Japanese Patent 2002-544296 discloses, Japanese Patent 2005-507961 Patent Laid while examples of using complexes having a crosslinked bisindenyl ligand, Japanese Patent Laid-Open 2-276807 and JP Japanese Patent 2002-308933, JP Japanese Patent 2004-292772, JP-Japan JP-8-311121 and JP Japanese Hei 8-311260 discloses, include Japanese Patent Laid-Open 8-48711 discloses such a catalyst combines the non-MAO modified particles in complex with crosslinked bisindenyl ligand examples to be used as, Japanese Patent 2004-292772 discloses the like, using a constrained geometry complex catalyst As, include Japanese Patent Laid-Open 6-306121 discloses such, as an example of using a combination of complexes having benzindenyl ligands and other low molecular weight polyethylene product complexes, Japanese Patent 2006-2098 JP etc. the.

In these methods, it is possible to control the quality and quantity of properly selected and long chain branching complex of the type and catalyst preparation conditions, the polymerization conditions. Further, the Japanese Patent Laid-Open 10-512600 discloses such, a method of introducing a long chain branched polyethylene chains with ethylene copolymerized dienes as a comonomer, in Japanese Kohyo 2008-505222 discloses such , it is also disclosed a method of introducing a long chain branched polyethylene chain by using T- reagent comprising chain transfer agent. In these methods, it is possible to control the quality and quantity of controls the type and amount of dienes and a chain transfer agent or, suitably selected or to long chain branching the catalyst type and polymerization conditions . Further, Japanese Patent Laid-Open 7-252311 and JP Japanese Hei 8-502303 discloses, WO 95-11931, Japanese Kohyo 2001-511215 discloses, Japanese Patent 2006-321991 Patent Laid the manufactures in advance macromonomer using a specific metallocene catalyst, a method of introducing a long chain branched polyethylene chains is disclosed by further copolymerizing this macromonomer and ethylene. In these methods, it is possible to control complex type and catalyst preparation conditions, polymerization conditions, the quality and quantity of properly selected and long chain branching the quantity and molecular weight of the macromonomer. Further, as an index representing the ethylene polymer having such long chain branching, generally has a melt flow rate ratio (MFR ratio: for example, see Japanese etc. Japanese Patent No. 2,571,280), melt tension (MT: e.g. see Japanese Patent No. 3425719 Publication), the presence or absence of rise of elongation viscosity (strain hardening) (e.g., see Japanese Japanese Patent No. 4190638, etc.), activation energy (e.g., Japanese Patent Laid-7- It is expressed in a variety of measurement techniques such as seen in 062,031 discloses such reference) and the like. In addition, as is actually commercially available resin, product name: AFFINITY (TM) FM1570 (manufactured by Dow Chemical Co., Ltd.), trade name: Excellen GMH (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd.), and the like .

However, ethylene polymers having long chain branching structure resulting in these methods are all not suitable ethylene polymer (B) as a component of the polyethylene resin composition of the present invention. By selecting a specific ethylene-based polymer (B), we that molding properties and mechanical strength of the shaped bodies according to the polyethylene-based compositions and the composition, the transparency results in significantly different results discovered, in addition to the selection of suitable long chain branched structure in the present invention, further, as previously described, MFR, density, ethylene polymer molecular weight distribution conditions are suitably designed (B) the by using as a component of a polyethylene-based composition, the first time the present invention reaches completion.
The ethylene polymer having a long chain branching structure can be generated in the prior art, as described above which, those using a Ziegler type catalyst was used complexes with bridged bis cyclopentadienyl ligand, crosslinked those using complexes having a bis-indenyl ligand, which was used as a catalyst in combination of a non-MAO modified particles in complex with crosslinked bisindenyl ligand, those using constrained geometry complex catalyst, benzoindenyl ligand the complexes with those used in combination with other low molecular weight polyethylene product complexes, obtained by introducing long chain branching into polyethylene chains with ethylene copolymerized dienes as a comonomer, use of the T- reagent comprising chain transfer agent and those obtained by introducing long chain branching into polyethylene chain, to produce a pre-macromonomer using a specific metallocene catalyst, a further The macromonomer and ethylene are copolymerized include those obtained by introducing long chain branching into polyethylene chains.

However, as the ethylene polymer in the present invention (B), in the case where using an ethylene copolymer prepared above Ziegler catalyst, spreading the molecular weight distribution and the copolymer composition distribution, the polyethylene resin composition and the or insufficient impact strength and transparency of the molded body, it can not be said tackiness to the low crystalline component is often preferable to or become severely. To further long long chain branched structure in the catalyst produces only a small amount, impact strength and transparency is not sufficiently improved, the complex having a complex or crosslinked bisindenyl ligand having a bridged bis cyclopentadienyl ligand when using the ethylene copolymer produced using, or there is insufficient impact strength and transparency of the polyethylene resin composition and the molded article due to the tendency of the molecular weight distribution is widened, long chain branching without the impact strength and transparency is sufficiently improved in the trend length becomes longer chain, ethylene made using as catalyst a combination of non-MAO modified particles in complex with crosslinked bisindenyl ligand when using the copolymer, the molecular weight distribution is insufficient impact strength and transparency of the polyethylene resin composition and molded product to tend to spread further than the case of MAO cocatalyst, In example, in the Excellen GMH is said to commercially produced by actually using the catalyst, a wide molecular weight distribution, long chain branching is long, since the number of branches is insufficient, the improvement in moldability effects or insufficient impact strength and transparency is not sufficiently improved, when using the ethylene copolymer produced using a constrained geometry complex catalyst, for example, by actually using the catalyst prepared in has been described above are said to commercially AFFINITY (e.g. FM1570), longer length of the long-chain branched chain, and, because the number of branches is insufficient, insufficient effect of improving the moldability or, impact strength and is not sufficiently improved transparency, even any of the above-mentioned method as it stands, not preferred as a method for producing ethylene polymer (B) in the present invention.

Also, if a complex having a benzindenyl ligands other low molecular weight polyethylene product complex in combination with ethylene copolymer produced using a length required for the ethylene polymer (B) in the present invention although the possibility of realizing chain branched structure appears to some extent with, the long-chain branched structure generation or limited to polymerization conditions at a low hydrogen concentration, the catalyst synthesis conditions of complex use ratio such as molecular weight distribution is not spread and further or studied is required polymerization conditions, Study MFR and density settings of the ethylene-based polymer (B) and combining the ethylene polymer (a) is required. Further, a method of copolymerizing a diene, by a method of utilizing a chain transfer agent, in order to achieve the appropriate long chain branched structure as the ethylene polymer (B) in the present invention, dienes to be used, chain transfer agent, must wait for further consideration of the type and polymerization conditions of a polymerization catalyst. Furthermore, the residual diene or residual contamination of the polymer by chain transfer agent (odor, coloration, deterioration) would need to be solved problems such as. Further, in order to achieve the appropriate long chain branched structure as ethylene polymer (B) in the present invention by a method of introducing a long chain branched polyethylene chain manufactures macromonomer copolymerized with ethylene, using polymerization catalyst type and polymerization conditions, the molecular weight of the produced macromer, density, copolymer ratio must wait for further consideration of the control of, and further, the remaining macromer polymer or during polymerisation as a low molecular weight polymer component to remain in the polyethylene resin composition to coalesce one component, the impact strength and transparency of the polyethylene resin composition and the molded article due to the tendency of the molecular weight distribution and the copolymer composition distribution is widened insufficient not sufficient preferable because there is likely to be. For this reason, as the ethylene-based polymer (B), without the impact strength and transparency not sufficiently improved tended to length of the long chain branching of chain becomes longer, the polymer of pollution (odor, coloring, deterioration), and the like of the problem is also considered that there is a need to be resolved.

That is, a result of inventors have conducted intensive studies in order to achieve the object of the present invention, as the olefin polymerization catalyst to produce a suitable long chain branched structure as ethylene polymer (B) of the present invention, an example as a recently discovered such crosslinking (cyclopentadienyl) (indenyl) how to use as an essential catalyst component complexes having a ligand such as (Japanese Patent 2011-137146 JP and herein [V ] leads to the production method of the ethylene-based polymer, etc.) of the present invention, also, as another example, a method of using a complex having a benzindenyl ligand such as the catalyst component (Japanese Patent 2006-2098 JP reaches the like), as yet another example, cross-linked bis metallocene complex (indenyl) ligand or bridged bis (azulenyl) ligand or bridged bis (cyclopentadienyl Eni ) Complexed with a ligand, it was led to a method of using a catalyst with a mixture of borane compounds or borate compound is a compound to produce an organoaluminum-oxy compound and a cationic metallocene compound.

The ethylene-based polymer (B) crosslinking (cyclopentadienyl) for generating a suitable long chain branched structure as (indenyl) olefin polymerization catalyst as an essential component complexes having a ligand of the present invention have the following They comprise components (a-1) and component (b) of further includes a desired component (c).
Component (a-1): General formula (a-1-1) a metallocene compound component represented by (b): component (a-1) of the metallocene compound and the reaction was to produce a cationic metallocene compound compound component (c ): particulate carrier

i) component (a-1)
Component (a-1) is a metallocene compound represented by the following general formula (a-1-1).

Figure JPOXMLDOC01-appb-C000012

Wherein (a-1-1), M represents any of the transition metals Ti, Zr or Hf. X 1 and X 2 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1 and Q 2 are each independently a carbon atom, a silicon atom or a germanium atom. R 1 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, form a four ring together with Q 1 and Q 2 and at least two members out of R 1 it may be. m is 0 or 1, when m is 0, Q 1 is directly bonded to the conjugated 5-membered ring containing R 2 and R 3. R 2 is independently a hydrogen atom, a halogen atom, having 1 to 20 carbon atoms hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6, from 1 to 20 carbon atoms halogen-containing hydrocarbon group, but a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, the following plurality of R 2 may be a hydrocarbon group or the like do not form a ring together with the bond to which carbon atoms as R 4. R 3 represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 4 is an atom or group bonded to the carbon atoms of R 3, each independently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 1 containing silicon atoms 1-6 ~ 18 silicon-containing hydrocarbon group, a halogen-containing hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms. n is 0 to an integer of 10, when n is 2 or more, at least two of R 4 may form a ring together with the bond to which carbon atoms. R 5 is independently a hydrogen atom, a halogen atom, having 1 to 20 carbon atoms hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6, from 1 to 20 carbon atoms halogen atom-containing hydrocarbon group, but a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, even more R 5 is a hydrocarbon group or the like do not form a ring together with the bond to which carbon atoms as R 4. ]

M in said general formula (a-1-1), a metallocene compound represents Ti, Zr or Hf. The M is preferably Zr or Hf, more preferably in terms of high polymerization activity M is Zr, in the present invention, for a description of all the metallocene complex since, in the central metal species suitable Ranking There are applied.

Further, X 1 and X 2 are each independently a hydrogen atom or a chlorine atom, a bromine atom, an iodine atom or a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxymethyl group, ethoxymethyl group, n- propoxymethyl group, i- propoxymethyl, n- butoxymethyl group, i- butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, an acetyl group, 1-oxopropyl group, 1-oxo -n- butyl group, 2- methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo - propyl group, a phenyl acetyl group, diphenylacetyl groups, Baie Benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, a 4-methoxyphenyl group, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-i- propyl aminomethyl group, bis (dimethylamino) methyl group, bis (di-i- propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methylimino group, ethylimino group, 1- (methylimino) ethyl group, 1- (phenylimino) ethyl , 1 - [(phenylmethyl) imino] ethyl group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, t-butoxy group, a phenoxy group, dimethylamino group, diethylamino group , di-n- propylamino group, di-i- propylamino group, di-n- butylamino group, di i - butylamino group, di-t- butylamino group, and a diphenylamino group.
Specific examples of preferred X 1 and X 2, a chlorine atom, a bromine atom, a methyl group, n- butyl group, i- butyl group, a methoxy group, an ethoxy group, i- propoxy, n- butoxy group, a phenoxy group, dimethylamino group, di-i- propylamino group. Among these specific examples, a chlorine atom, a methyl group, a dimethylamino group is particularly preferred.
Also, Q 1 and Q 2 are each independently a carbon atom, a silicon atom or a germanium atom. Preferably a carbon atom or a silicon atom.

Furthermore, as the R 1, each independently, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , neopentyl group, cyclopentyl group, n- hexyl group, a cyclohexyl group, and a phenyl group. Further, as a case where R 1 forms a ring together with Q 1 and Q 2, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group cyclohexylene, sila cyclobutyl group, silacyclopentyl group, silacyclohexyl groups such as and the like.
Specific examples of preferred R 1, when Q 1 or / and Q 2 is a carbon atom, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, include cyclobutylidene group, also, Q 1 or / and Q 2 If it is a silicon atom, a methyl group, an ethyl group, a phenyl group, and silacyclooctane butyl group.

Further, R 2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t - butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5 - dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo Cyclopentyl, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6 - pentafluorophenyl group, 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethylsilyl group , triphenylsilyl group, diphenylmethyl silyl group, and a phenyl dimethylsilyl group.

Also, one of the two R 2, at least one of a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen having 1 to 20 carbon atoms containing hydrocarbon group, if it is a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, particularly polymerization activity becomes higher, preferably. Further, when the 2-position of the R 2 is a hydrogen atom, particularly preferably from the viewpoint of excellent formability because the characteristics of the long-chain branched structure is improved.
Preferred specific examples of R 2 are each independently a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, 2-methyl-furyl group, and a trimethylsilyl group.
Among these specific examples, a hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, more preferably a trimethylsilyl group, a hydrogen atom, a methyl group, a phenyl group is particularly preferred.

Specific examples of the condensed cyclopentadienyl structure formed from a cyclopentadienyl moiety and R 3 wherein R 3 is attached include the following partial structure (I) ~ (VI).
Among these specific examples, (I), (III), (VI) are preferred. Also, on these partial structures (I) ~ (VI), R 4 may be substituted.

Figure JPOXMLDOC01-appb-C000013

R 4 substituents, in addition to a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-t-butyl phenyl group, 3,5-dimethylphenyl group, 3,5-di -t- butyl phenyl group, a naphthyl group, anthracenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl Group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2, 3,4,5,6 pentafluorophenyl group, 2,6-dichloro-4-trimethylsilyl phenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, tri phenyl silyl group, diphenylmethyl silyl group, and a phenyl dimethylsilyl group.
Further, in R 4 is 2 or more, as an example of a case of forming a ring together with the bond to which carbon atoms, benzo [e] indenyl, benzo [f] indenyl, 6,7-dihydro inductor Seniru group, 5,5,7,7- tetramethyl-6,7-dihydro-indanyl cell group, 5,6,7,8-tetrahydro - benzo [f] indenyl, 5,6,7,8 tetrahydro-5,5,8,8-tetramethyl - such as benzo [f] indenyl group.
Specific examples of preferred R 4, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group , naphthyl group, and a trimethylsilyl group.

Also, R 5 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t - butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5 - dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo Cyclopentyl, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6 - pentafluorophenyl group, 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethylsilyl group , triphenylsilyl group, diphenylmethyl silyl group, and a phenyl dimethylsilyl group.
Further, of the four R 5, at least one halogen hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6, 1 to 20 carbon atoms of 1 to 20 carbon atoms containing hydrocarbon group, if it is a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, particularly polymerization activity becomes higher, preferably. Further, when the 2-position and 5-position of R 5 is hydrogen atom, particularly preferably from the viewpoint of excellent formability because the characteristics of the long-chain branched structure is improved.
Preferred specific examples of R 5 include a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group , phenyl group, 2-methyl-furyl group, and a trimethylsilyl group.
Among these specific examples, a hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, more preferably a trimethylsilyl group, a hydrogen atom, a methyl group, t- butyl group, a phenyl group is particularly preferred.

Further, in the general formula (a-1-1), m is 0 or 1, when m is 0, Q 1 is directly bonded to the conjugated 5-membered ring containing R 2 and R 3. Furthermore, n is 0 to an integer of 10, when n is 2 or more, at least two of R 4 may form a ring together with the bond to which carbon atoms.

Metallocene compound of the component (a-1) is preferably one represented by the following general formula (a-1-2), which is more preferable that the following general formula (a-1-3).

Figure JPOXMLDOC01-appb-C000014

In the metallocene compound represented by the general formula (a-1-2), and (a-1-3), X 1 , X 2, Q, R 1, R 2, R 4 and R 5 are described above the same structure as the atoms and groups indicated in the description of the metallocene compound represented by the general formula (a-1-1), can be selected.

Specific examples of the metallocene compound of the component (a-1), are shown in the following Table a-1 ~ Table a-4, not limited thereto. In Table a-1 ~ Table a-4, Cp is a cyclopentadienyl group, Ind is an indenyl group, Me is methyl, Ph is phenyl, Et is an ethyl group, nPr is n- propyl, nBu is n- butyl group, nC5 the normal pentyl group, nC6 the normal hexyl group, Bz is a benzyl group, Azu represents azulenyl.

Figure JPOXMLDOC01-appb-T000015

Figure JPOXMLDOC01-appb-T000016

Figure JPOXMLDOC01-appb-T000017

Figure JPOXMLDOC01-appb-T000018

Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like.
Further, when the use of these metallocene compounds as the component (a-1), it is also possible to use two or more kinds.

In the inside of the specific compounds illustrated above, it shows the preferred metallocene compounds as the component (a-1) below.
That is, dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (Shikuropentaji enyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butyl-indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl indenyl) Jill Niumujikurorido, isopropylidene (cyclopentadienyl) (3-n-butyl-indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl ) (3-t-butyl-indenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (4-phenyl indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzo [e] indenyl) zirconium dichloride, isopropylidene isopropylidene (cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, cyclobutylidene cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, Jimechiruge Millen (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( azulenyl) zirconium dichloride, dimethylsilylene (4-t-butyl-cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (4-t-butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, dimethylsilylene (4-t-butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dimethyl, dimethylsilylene (4-t-butyl cyclopentadienyl Yl) (4-phenyl indenyl) zirconium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dimethyl, dimethylsilylene (4-t-butyl-cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene zirconium (4-t-butyl-cyclopentadienyl) (azulenyl) zirconium dichloride and the compound, the compound was replaced with titanium or hafnium, as like are preferable, and the like.

Further, in the inside of the specific compounds illustrated above as the metallocene compound as the component (a-1), it shows particularly preferred are set forth below.
Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclo pentadienyl) (3-phenyl indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (4-phenyl indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (benzo [e] indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-Buchiruindeni ) Zirconium dichloride, isopropylidene (cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, dimethyl gel Mi (cyclopentadienyl) (indenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3 -t- butyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3-t-butyl-indenyl) hafnium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (4-t-butyl Cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dimethyl, and the like.

ii) component (b)
Exemplified as olefin polymerization catalysts ethylene polymer (B) as to produce a suitable long chain branched structure crosslinking (cyclopentadienyl) (indenyl) essential component complexes having a ligand such as of the present invention olefin polymerization catalyst may contain, in addition to the above components (a-1), metallocene compound of the component (a-1) cationic by reacting (component (a-1), hereinafter, also simply., referred to as the a) compound forming the metallocene compounds containing (component (b), hereinafter, also. be simply referred to as b).

One of the metallocene compound (a) reacts with to form a cationic metallocene compound (b), and organic aluminum oxy compound.
The organoaluminum oxy-compound, in the molecule, having Al-O-Al bonds, the number of bonds is usually 1 to 100, preferably in the 1-50 range. Such organoaluminum oxy-compounds are usually product obtained by reacting with water the organic aluminum compound.
Among the organic aluminum oxy compound as described above, those obtained by reacting an alkyl aluminum and water, usually referred to as aluminoxanes, (including those consisting essentially of methylaluminoxane (MAO)) particularly methylaluminoxane as the organoaluminum oxy compound, it is preferred.

Further, as another specific example of the compound which reacts with the metallocene compound (a) to form a cationic metallocene compound (b), it includes the borane compounds and borate compounds.
Expressed more specifically the borane compounds, triphenyl borane, tri (o-tolyl) borane, tri (p- tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris ( p- fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl), tris ( perfluoroanthryl) borane, tris (Pafuruorobi Fuchiru) such as borane and the like.

Further, specific representative of a borate compound, the first example is a compound represented by the following general formula (b-1).
[L 1 -H] + [BR 6 R 7 X 4 X 5] - ··· formula (b-1)
Wherein (b-1), L 1 is a neutral Lewis base, H is a hydrogen atom, [L 1 -H] is ammonium, anilinium, a Bronsted acid such as phosphonium.
The ammonium, trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, trialkyl-substituted ammonium, such as tri (n- butyl) ammonium, di (n- propyl) ammonium, can be exemplified dialkylammonium such as dicyclohexylammonium.
As the anilinium, N, N- dimethylanilinium, N, N- diethyl anilinium, N, N-2,4,6 N such pentamethyl anilinium, N- dialkylanilinium can be exemplified.
Further, as the phosphonium, triphenyl phosphonium, tributyl phosphonium, tri (methylphenyl) phosphonium, triaryl phosphonium and tri (dimethylphenyl) phosphonium, and trialkyl phosphonium.

In the formula (b-1), R 6 and R 7 are each independently 6-20, preferably carbon atoms of 6 to 16, the same or different aromatic or substituted aromatic hydrocarbon group in, may be linked to each other by a bridging group, as the substituent of the substituted aromatic hydrocarbon group, an alkyl group or a fluorine typified methyl group, an ethyl group, a propyl group, isopropyl group, chlorine, bromine, halogen atoms iodine are preferred.
Furthermore, X 4, and X 5 each independently hydride radicals, halide radicals, hydrocarbon group containing from 1 to 20 carbon atoms, the carbon of the the 1 to 20 substituted with one or more hydrogen atoms by a halogen atom a substituted hydrocarbon group containing an atom.

The above Examples of the compound represented by formula (b-1), tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3, 5-ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoro-naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2, 6 ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6 Jifuruorofu Yl) borate, dimethylanilinium tetra (perfluoro-naphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5 - ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoro-naphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyl Tetra (perfluoro-naphthyl) borate, tripropyl ammonium tetra (pentafluorophenyl) borate, tripropyl ammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropyl ammonium tetra (perfluoro-naphthyl) borate, di (1 - propyl) ammonium tetra (pentafluorophenyl) borate, and the like can be exemplified dicyclohexylammonium tetraphenylborate.

Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (perfluoro-naphthyl) borate is preferred.

The second example of the borate compound is represented by the following general formula (b-2).
[L 2] + [BR 6 R 7 X 4 X 5] - ··· formula (b-2)
Wherein (b-2), L 2 is a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert- butyl cation, pentyl cation, tropicity cation, benzyl cation, trityl cation , sodium cations, protons, and the like.
Further, R 6, R 7, X 4 and X 5 are as defined in each of the general formula (b-1).

Specific examples of the compounds, trityl tetraphenylborate, trityl tetra (o-tolyl) borate, trityl tetra (p- tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, trityl tetra (p- fluorophenyl) borate, trityl tetra (m-fluorophenyl) borate, trityl tetra (3,5-difluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, trityl tetra (2,6-di-fluoro methylphenyl) borate, trityl tetra (3,5-ditrifluoromethylphenyl) borate, trityl tetra (perfluoro-naphthyl) borate, tropicity tetraphenylborate, tropicity tetra (o-tolyl) Rate, Tropi tetra (p- tolyl) borate, tropicity tetra (m-tolyl) borate, tropicity tetra (o-fluorophenyl) borate, tropicity tetra (p- fluorophenyl) borate, tropicity tetra (m- fluorophenyl) borate, tropicity tetra (3,5-difluorophenyl) borate, tropicity tetra (pentafluorophenyl) borate, tropicity tetra (2,6-ditrifluoromethylphenyl) borate, tropicity tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) borate, NaBPh 4, NaB (o- CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) 4, Na B (o-F-Ph) 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) 4, NaB (2,6- (CF 3 ) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H + BPh 4 · 2 diethyl ethers, H + B (3,5-F 2 -Ph) 4 · 2 diethyl ether, H + B (C 6 F 5) 4 - · 2 diethyl ether, H + B (2,6- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (3,5- (CF 3) 2 -Ph) 4 · 2 diethyl ether, can be exemplified H + B (C 10 H 7 ) 4 · 2 diethyl ether it can.

Among these, trityl tetra (pentafluorophenyl) borate, trityl tetra (2,6-ditrifluoromethylphenyl) borate, trityl tetra (3,5-ditrifluoromethylphenyl) borate, trityl tetra (perfluoro-naphthyl) borate, Tropi tetra (pentafluorophenyl) borate, tropicity tetra (2,6-ditrifluoromethylphenyl) borate, tropicity tetra (3,5-ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) borate, NaB (C 6 F 5) 4 , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H + B (C 6 F 5 ) 4 - · 2 diethyl Ether, H + B (2,6- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (3,5- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B ( C 10 H 7) 4 · 2 diethyl ether.

More preferably, among these, trityl tetra (pentafluorophenyl) borate, trityl tetra (2,6-ditrifluoromethylphenyl) borate, tropicity tetra (pentafluorophenyl) borate, tropicity tetra (2,6-di trifluoromethylphenyl) borate, NaB (C 6 F 5) 4, NaB (2,6- (CF 3) 2 -Ph) 4, H + B (C 6 F 5) 4 - · 2 diethyl ether, H + B (2,6- (CF 3) 2 -Ph ) 4 · 2 diethyl ether, H + B (3,5- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (C 10 H 7) 4-2 diethyl ether.

As the catalyst component (b), the use of borane compounds and borate compounds, since the polymerization activity and copolymerizability is high, productivity is improved ethylene polymer having long chain branching.
Further, as another specific example of the metallocene compound (a) reacts with the cationic metallocene compound to form compound (b), clay mineral, the layered silicate compound, chemically treated solid oxide.
Further, as component (b), and the organoaluminum oxy-compound, it is possible to use a mixture of the borane compound and a borate compound, a long chain branched structure desired for the ethylene polymer (B) in the present invention to improve the characteristics, it is preferably used in combination with the organoaluminum oxy-compound the borane compounds and borate compounds. Furthermore, the borane compound and the borate compound can also be used in combinations of two or more.

iii) component (c)
Exemplified as olefin polymerization catalysts ethylene polymer (B) as to produce a suitable long chain branched structure crosslinking (cyclopentadienyl) (indenyl) essential component complexes having a ligand such as of the present invention olefin polymerization catalyst, particulate carrier (component (c), hereinafter, may be simply referred to as c.) preferably contains.

The particulate carrier as the component (c), inorganic carriers include particulate polymer carrier or a mixture thereof. Mineral support is a metal, metal oxide, metal chloride, metal carbonate, carbonaceous material or a mixture thereof, can be used.
Suitable metals which can be used in mineral support, for example, iron, aluminum, nickel, or the like.

Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Tables 1 to 14 elements can be mentioned, for example, SiO 2, Al 2 O 3 , MgO, CaO, B 2 O 3, TiO 2, ZrO 2, Fe 2 O 3, Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · SiO 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2, Al 2 O 3 · CuO, Al 2 O 3 · Fe 2 O 3, Al 2 O 3 · NiO, can be exemplified a variety of natural or synthetic, such as SiO 2 · MgO alone oxide or composite oxide.
Here, the above equation is not a molecular formula, a represents the only composition, structure and component ratio of the composite oxide used in the present invention is not limited in particular.
The metal oxide used in the present invention is not safe to have absorbed a small amount of water, also contain small amounts of impurities no problem.

As metal chloride, for example, an alkali metal chloride of an alkaline earth metals are preferred, particularly such as MgCl 2, CaCl 2 is especially preferred.
As the metal carbonate, alkali metal, alkaline earth metal carbonates are preferable, specifically, magnesium carbonate, calcium carbonate and barium carbonate.
The carbonaceous material, for example, carbon black, activated carbon and the like.
Or mineral support, each of which may be suitably used for the present invention, in particular metal oxides, silica, the use of such alumina preferred.

An example of an olefin polymerization catalyst and the ethylene based polymer (B) as a preferred long chain branched structure complex essential components having a benzindenyl ligand or the like for generating the above invention, the following components (a- and 2) it is specifically exemplified as an olefin polymerization catalyst comprising the above-mentioned components (b) and the preferred component (c).

iv) component (a-2)
Component (a-2) is represented by the following general formula (a-2-1) with benzindenyl ligands one or more indicated, preferably 2 or more, more preferably a metallocene compound having three.

Figure JPOXMLDOC01-appb-C000019

Where the substituents R 8 ~ R 13 are each independently a trialkyl silicon radical or a hydrogen atom with a hydrocarbon group, hydrocarbon substituents having 1 to 30 carbon atoms having 1 to 30 carbon atoms. Specific examples of the hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an alkyl group such as a cyclohexyl group; a vinyl group, an alkenyl group such as allyl group; a phenyl group, a dimethylphenyl group , diethyl phenyl group, dipropylphenyl group, dibutylphenyl group, trimethylphenyl group, triethylphenyl group, tripropyl phenyl group, tributylphenyl group, a biphenyl group, a naphthyl group, an aryl group such as an anthryl group; trityl group, phenethyl group, benzhydryl group, phenylpropyl group, phenylbutyl group, an arylalkyl group such as neophyl group, and an arylalkenyl group such as styryl group. These groups may have branches. Also, the substituents R 8 ~ R 13, 2 substituents adjacent may form a ring together with the carbon atom bonded. Further, component (a-2) is, if it has a ligand having a three cyclopentadienyl skeleton, including the benzoindenyl ligand, at least two of them, a hydrocarbon group, a silylene group a substituted silylene group or the like, the same crosslinking group composed of Q 1, Q 2, R 1 as defined in the above general formula (a-1-1), cross-linked with ethylene bridging group and dimethylsilylene bridging group such as metallocene complex is also effective. The center transition metal and the central transition metal to groups other than the ligand having a cyclopentadienyl skeleton bound (auxiliary ligand) is a hydrocarbon group, an alkoxyl group, a halogen atom, such as a hydrogen atom, the formula ( M defined in a-1-1), the same thing applies with X 1, X 2.

Specific examples of the component (a-2), the central transition metal is exemplified as the case of Zr, it was as shown in Table a-5 and Table a-6. In Table a-5 and Table a-6, Cp is a cycloalkyl Bae Ntajieniru group, Ind is an indenyl group, Bzind is a benzoindenyl group, Dbi dibenzo indenyl group, Me represents a methyl group, Bu a butyl group represent.

Figure JPOXMLDOC01-appb-T000020

Figure JPOXMLDOC01-appb-T000021

Specific preferred examples of the component (a-2) is, Bzind 3 ZrH, Dbi 3 ZrH , Bzind 2 CpZrH, Bzind 2 (1,3-Me 2 Cp) ZrH, Bzind 2 (1-Bu-3-MeCp) ZrH, Bzind 2 IndZrH, BzindInd 2 ZrH, Dbi 2 CpZrH, DbiCp 2 ZrH, Dbi 2 IndZrH, DbiInd 2 ZrH, Bzind 2 DbiZrH, BzindDbi 2 ZrH, BzindDbiCpZrH, BzindDbiIndZrH, Et (Ind) 2 BzindZrH, Et (Ind) 2 DbiZrH, Me 2 SiCp 2 BzindZrH, Me 2 SiCp 2 DbiZrH, Me 2 Si (Cp) (Ind) DbiZrH, Et (Bzind) 2 CpZrH, Et (Zind) is 2 IndZrH, more preferred examples, Bzind 3 ZrH, Dbi 3 ZrH , Bzind 2 CpZrH, Bzind 2 (1,3-Me 2 Cp) ZrH, Bzind 2 (1-Bu-3-MeCp) ZrH a Bzind 2 IndZrH, BzindInd 2 ZrH, Dbi 2 CpZrH, DbiCp 2 ZrH, Dbi 2 IndZrH, DbiInd 2 ZrH, Bzind 2 DbiZrH, BzindDbi 2 ZrH, BzindDbiCpZrH, BzindDbiIndZrH.

As described above, as the component (a-2) together with the component (b), but like the organoaluminum oxy-compound is used, also in combination with the organoaluminum oxy-compound the borane compound and the borate compound in the present case it is a characteristic of the long-chain branched structure desired for the ethylene polymer (B) in the present invention preferably the enhanced, similarly, the other than component (b) component (a-2), component (c) it is also preferable to include.

Bridged bis generating a suitable long chain branched structure as ethylene polymer of the present invention (B) (indenyl) ligand or bridged bis (azulenyl) ligand or bridged bis (cyclopentadienyl) ligands a complex having, an example of an olefin polymerization catalyst to the mixture as an essential component of the borane compound or the borate compound is a compound to produce an organoaluminum-oxy compound and a cationic metallocene compound, the following components (a-3), specifically exemplified as a mixture and olefin polymerization catalyst comprising the above-described preferred components (c) and the organoaluminum oxy-compound and borane compounds or borate compounds described in the above component (b).
Here, bridged bis (indenyl) ligand or bridged bis (azulenyl) ligand or bridged bis (cyclopentadienyl) complexes having a ligand (each component (a-3-1), (a-3 -2), (to.) the a-3-3), in the classification of the metallocene compounds mentioned in the paragraph of the above 1-6 (ii) a metallocene catalyst, as represented by the general formula [2] Do, be the same or different two or cyclopentadienyl ring or two indenyl rings may be the same or different is referred to complex having a basic skeleton crosslinked with a crosslinking group Q 1. The cyclopentadienyl ring, indenyl ring, azulenyl ring, substituents which may have crosslinking groups Q 1 is, has a high degree of freedom as long as they do not inhibit the basic skeleton structure, for example, Japanese Kohyo 2002 metallocene complex having a monocyclic or polycyclic heteroaromatic group containing a heteroatom -535339 JP as a substituent on a conjugated five-membered ring structure ligand also preferably used.

Figure JPOXMLDOC01-appb-C000022

[Wherein, A 3 and A 4, a ligand having a conjugated five-membered ring structure (or A 3 and A 4 are identical or different in the same compound), Q 1 is two conjugated five-membered a binding group which crosslinks the cyclic ligands at an optional position, M is a metal atom selected from group 4 of the periodic table, and X and Y are each independently a hydrogen atom bound to M, a halogen atom a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, respectively. ]

Specific examples of complexes having bridged bis (indenyl) ligand of component (a-3-1), if the center transition metals are exemplified as the case of Zr,
(I) of the formula [2] a compound represented by denotes a compound of structure binding group Q 1 is shown below for example in the following Table a-7 ~ Table a-9. In Table a-7 ~ Table a-9, Ind is an indenyl group, TMS represents a trimethylsilyl.

As (I-1) Q 1 is an alkylene group, include the compounds described in the following Table a-7.

Figure JPOXMLDOC01-appb-T000023

(I-2) Q 1 is as silylene group, include the compounds described in the following Table a-8. In Table a-8, Ind is an indenyl group, BenInd the benzoindenyl group, PhInd phenyl indenyl group, TMSPh represents a trimethylsilyl phenyl group.

Figure JPOXMLDOC01-appb-T000024

(I-3) Q 1 is germanium, phosphorus, nitrogen, as the hydrocarbon group containing boron or aluminum include compounds described in the following Table a-9. In Table a-9, Ind is an indenyl group, PhInd phenyl indenyl group, TMSPh represents a trimethylsilyl phenyl group.

Figure JPOXMLDOC01-appb-T000025

Specific examples of complexes having bridged bis (azulenyl) ligand component (a-3-2), if the center transition metals are exemplified as the case of Zr,
(II) of the formula [2] a compound represented by denotes a compound of structure binding group Q 1 is shown below for example in the following Table a-10 ~ Table a-12.

As (II-1) Q 1 is an alkylene group, include the compounds described in the following Table a-10. In Table a-10 ~ Table a-12, tBuPh is tributylphenyl group, TMSPh trimethylsilyl phenyl group, Naph naphthyl group, BiPh biphenyl group, Azu represents azulenyl group, ClPh the chlorophenyl group.

Figure JPOXMLDOC01-appb-T000026

(II-2) Q 1 is as silylene group, include the compounds described in the following Table a-11.

Figure JPOXMLDOC01-appb-T000027

(II-3) Q 1 is germanium, phosphorus, nitrogen, as the hydrocarbon group containing boron or aluminum include compounds described in the following Table a-12.

Figure JPOXMLDOC01-appb-T000028

Specific examples of complexes having bridged bis (cyclopentadienyl) ligands components (a-3-3), if the center transition metals are exemplified as the case of Zr,
(III) of the formula [2] a compound represented by denotes a compound of structure binding group Q 1 is shown below for example in the following Table a-13 ~ Table a-16. In Table a-13 ~ Table a-16, Cp is cyclopentadienyl group, TMS is trimethylsilyl, Flu represents fluorenyl.

As (III-1) Q 1 is an alkylene group, include the compounds described in the following Table a-13.

Figure JPOXMLDOC01-appb-T000029

(III-2) Q 1 is as silylene group, include the compounds described in the following Table a-14 and Table a-15.

Figure JPOXMLDOC01-appb-T000030

Figure JPOXMLDOC01-appb-T000031

(III-3) Q 1 is germanium, phosphorus, nitrogen, as the hydrocarbon group containing boron or aluminum include compounds described in the following Table a-16.

Figure JPOXMLDOC01-appb-T000032

In these bridged bis defined (indenyl) ligand or bridged bis (azulenyl) ligand or bridged bis (cyclopentadienyl) ligand metallocene complex, a mixture of an organic aluminum oxy compound and borane compounds such as the combination catalysts, suitable long chain branched structure as ethylene polymer of the present invention (B) is applied to the ethylene polymer (B).

Above, as a preferred embodiment of the olefin polymerization catalyst to produce a suitable long chain branched structure as ethylene polymer (B) of the present invention, the crosslinking (cyclopentadienyl) (indenyl) complex having a ligand such as the catalyst system as an essential component, a catalyst system for the complex essential components having a benzoindenyl ligand or the like, a bridged bis (indenyl) ligand or bridged bis (cyclopentadienyl) ligand metallocene complex a complex having, said three of the catalytic system using a mixture of a borane compound or a borate compound is a compound to produce an organoaluminum-oxy compound and a cationic metallocene compound. Among these, crosslinked (cyclopentadienyl) (indenyl) and catalyst system as an essential component complexes having a ligand such as a metallocene complex bridged bis (indenyl) ligand or bridged bis (cyclopentadienyl ) complexed with a ligand, more preferably the catalyst system using a mixture of a borane compound or a borate compound is a compound to produce an organoaluminum-oxy compound and a cationic metallocene compounds, crosslinking (cyclopentadienyl) the catalyst system according to the complex with (indenyl) ligand, such as essential component are more preferable.

In the present invention, the production of ethylene polymer (B) is preferably the above olefin polymerization catalyst (i) ~ (iv), more preferably (i), (ii), (iv), more preferably (i ), (ii), particularly preferably in contact with the ethylene (ii) a metallocene catalyst, it is carried out by polymerizing or copolymerizing ethylene. Olefin polymerization catalysts may be used a plurality of types among (i) ~ (iv). In performing the polymerization or copolymerization of ethylene, the polymerization method in the section preparation of ethylene polymer described above (A), the ethylene raw material, polymerization medium, polymerization temperature, etc., the polymerization process or the like, description reference is all about scavengers . However, taking into account the properties and olefin polymerization catalyst characteristics to be used to wish ethylene-based polymer (B), it is needless to say that these conditions settings need to be optimal. For example, a lower MFR, when desired low density ethylene polymer (B) is to set the chain transfer agent concentration lower, or set a higher α- olefin concentration, polymerization in the production process thereof the order to prevent troubles such as sticking-occlusion, various operating temperature or set to a low temperature side commensurate with the melting temperature of the polymer, dissolution hardly occurs propane polymer in slurry polymerization, such as butane to select the low molecular weight hydrocarbon solvents, or select a gas phase polymerization without using a solvent, to select the solution polymerization of handling the polymer in solution. Also, if you want allowed confer significant long chain branching characteristics, as chain transfer reactions other than hydrogen is promoted, low monomer concentration conditions, high polymer concentration condition, a low scavenger concentration conditions, high temperature polymerization conditions, long polymerization it is preferable to select aggressively conditions, and the like.

(3) Other components (C)
Polyethylene resin composition of the present invention, besides being an essential component ethylene polymer (A) and the ethylene-based polymer (B), does not impair the object of the present invention, compounding the following substances as optional components be able to.

3-1. Besides other ethylene polymer ethylene polymer (A) and the ethylene-based polymer (B), high density polyethylene, low density polyethylene, high-pressure polyethylene, polar monomer graft-modified polyethylene, ethylene-based wax, ultra high molecular weight polyethylene various ethylene polymers such as ethylene-based elastomer and a modified product thereof can be used. The addition of high density polyethylene, rigidity, heat resistance, preferred for improving the impact strength and the like. The addition of low density polyethylene, flexibility, impact strength, easy adhesion, transparency, preferred for improving the low-temperature strength or the like. The addition of high-pressure polyethylene is flexible, easy adhesion, transparency, preferred for improving low-temperature strength, moldability and the like. Maleic acid modified polyethylene, ethylene-acrylic acid derivative copolymer, addition of polar monomer graft-modified polyethylene and ethylene-vinyl acetate copolymer, flexible, easy adhesion, coloring, various materials affinity, gas barrier properties, etc. It preferred to improve. The addition of ethylene wax, coloring, various materials affinity preferred to improve the moldability or the like. The addition of ultra high molecular weight polyethylene are preferred for improved mechanical strength, abrasion resistance and the like. The addition of ethylene-based elastomers, flexible, mechanical strength, preferred for improving the impact strength and the like.

3-2. Other olefin polymer ethylene polymer other than olefin polymer, such as polypropylene resins, polybutene, polyisobutene, higher olefin resin such as polyhexene, olefin rubbers, butadiene, isoprene, polybutadiene resins chloroprene, polystyrene, polystyrene resin poly α- methylstyrene, various cyclic olefin resin, and their modified products can be used.

3-3. Various resin mainly composed of other resin The ethylene-based polymers and other olefin polymers other than polymers can be used. Specifically, various nylon resin, various polyamide, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), various polyester, polycarbonate resin, EVOH, EVA, PMMA, PMA, various engineering plastics, such as polylactic acid, celluloses, natural gums, polyurethane, vinyl chloride, Teflon fluorocarbon resins such as, inorganic polymers such as silicone resins, and the like.

3-4. Additives Any additive may be appropriately used alone or in combination. Specifically, antioxidants (phenol-based, phosphorus-based, sulfur-based, etc.), ultraviolet absorbers, ultraviolet inhibitor, a light stabilizer, weathering agent, lubricant, antistatic agent, antifogging, anti-blocking agents, processing aids such as dispersants, coloring pigments (organic or inorganic pigments), pearl pigments, polarizing pearl pigments, crosslinking agents, foaming agents, neutralizing agents, heat stabilizers, nucleating agent, inorganic or organic filler filler [calcium carbonate, talc, metal powders (aluminum, copper, iron, lead), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc.], a flame retardant, etc. is used Kano it is.

(4) polyethylene resin composition of the mixture present invention of each component constituting the polyethylene resin composition of the present invention, as an essential component an ethylene polymer (A) and the ethylene-based polymer (B), optionally is prepared by mixing a substance (C) is a component.
The mixing ratio of each component, ethylene polymer (A) and of 41 to 99% by weight, ethylene polymer (B) is that 1-59 wt%, preferably, ethylene polymer (A) is 61 and to 96% by weight, ethylene polymer (B) is 4 to 39 wt%, more preferably, ethylene polymer (a) and a 69 to 96% by weight, ethylene polymer (B) is 4 a ~ 31 wt%, more preferably, ethylene polymer (a) and 69 - 91 wt%, is 9 to 31 wt% ethylene-based polymer (B), especially preferably, ethylene polymer (a) and 75 to 89 wt%, ethylene polymer (B) is 11 to 25 wt%. When the ethylene polymer (A) is too large, decrease in impact resistance and transparency of the polyethylene resin composition and molded articles thereof, of the moldability, the melt tension decreases, less and rigidity deteriorate and, among the moldability, melt extrusion is deteriorated. Further, when the ethylene polymer (B) is too large, it reduces the rigidity and transparency of the polyethylene resin composition and molded articles thereof, of the moldability, melt extrusion deteriorates less as tear strength , impact strength, not transparency improvement, among moldability, the melt tension decreases. The ratio of the substance (C) is an optional component is appropriately set within a range that does not impair the object of the present invention, generally 0-49 percent by weight, in particular the additive according to the 3-4 wherein in use of the known polyethylene resin, polyethylene resin composition, all of the existing examples of their application to the molded body is referenced.

The polyethylene resin composition of the present invention, upon an essential ingredient the above ethylene-based polymer (A) and the ethylene polymer (B), and by mixing the substance (C) is an optional component manufacturing, There is no particular restriction on the mixing method and equipment used, usually, a Henschel mixer, super mixer, after mixing with a tumbler type mixer or the like, single or twin screw extruder, a kneader, a plunger mixing extrusion extruder machine, and heated and kneaded in a Banbury mixer or the like, and pelletized. On heating and kneading, a liquid, a solvent in the presence of a gas, can be carried out in the absence. There is no particular limitation to the order of mixing the components, for example, it can be exemplified the following method (D-1) ~ (D-4).
(D-1) the ethylene polymer (A), the ethylene-based polymer (B), in all any substance (C) a solid state, preferably all in powder or grain or pellet form, previously contacted mixture Place, a method for a more uniform state by heating and kneading.
(D-2) ethylene polymer (A), the ethylene-based polymer (B), after any any one or more of the molten state or dissolved state or liquid state substance (C), and other components contacting a mixture, further a method for a more uniform state by heating and kneading.
(D-3) an ethylene polymer (A), by a method such as an ethylene-based polymer (B), any two, for example, any of the above materials (C) (D-1) or (D-2) preheated kneading, and further the remaining one component mixture obtained in the heating and kneading, a method for a more uniform state by heating and kneading.
(D-4) Ethylene polymer (A), by a method such as an ethylene-based polymer (B), for example the one of any substance (C) (D-1) or (D-2) each separately preheated and kneaded in both the remaining two, the mixture together obtained by further heating and kneading, a method for a more uniform state by heating and kneading.

(5) polyethylene resin composition of the properties present invention of the polyethylene resin composition of the present invention is an essential component ethylene polymer (A) and the ethylene polymer (B), and an optional component substances ( the C), the (D-1) are produced by mixing in a mixing process such as a ~ (D-4), as the physical properties, MFR described below in the entire composition, it must satisfy the range of density there is.

5-1. MFR
The melt flow rate of the polyethylene resin composition of the present invention (MFR) is, 0.05 ~ 50 g / 10 min, preferably 0.1 ~ 20 g / 10 min, more preferably 0.3 ~ 10 g / 10 min, further preferably 0.4 ~ 5.0 g / 10 min, particularly preferably 0.5 ~ 3.0 g / 10 min. MFR is poor fluidity of the polyethylene resin composition is less than 0.05 g / 10 min, or too high motor load of the extruder, since poor spreadability undesirable. MFR of 50 g / 10 min impact strength larger than the polyethylene-based resin composition and molded article is not preferable because mechanical strength and moldability, such as tear strength and the tensile strength is poor. Incidentally, MFR is a value when measured under the same conditions as the above conditions (A-1).

5-2. Density Density of the polyethylene resin composition of the present invention, 0.910 ~ 0.960g / cm 3, preferably 0.910 ~ 0.950g / cm 3, more preferably 0.916 ~ 0.940g / cm 3, more preferably 0.919 ~ 0.938g / cm 3, particularly preferably 0.920 ~ 0.936g / cm 3, most preferably from 0.921 ~ 0.934g / cm 3.
If the density of the polyethylene resin composition is less than 0.910 g / cm 3, or rigidity becomes low and the polyethylene resin composition and molded article, or become easy to tackiness, thin product of the thickness of the film or sheet like molding for body, various disadvantages, of course in the product use, product winding process, not preferable or inferior to the automatic bag-making machine aptitude because inconvenience in the process step after such surface printing and lamination, product pipes for various containers such as thick molded body, for the product is too soft deformation, since the forced the large thickness design than necessary is not preferable. The density of the polyethylene resin composition is higher than 0.960 g / cm 3, reduces the impact strength of the polyethylene resin composition and the molded article, even worse transparency. The density refers to a value measured under the same conditions as the above conditions (A-2).

Molding of polyethylene resin composition of the molded article and use the present invention [II] polyethylene resin composition of the present invention is that by molding the polyethylene resin composition of the present invention described above [I] manufactured, a method of molding is conventionally known injection molding, compression injection rotational molding, extrusion molding, blow molding, blow molding, polyolefin resin such as equal, all molding a polyolefin resin composition it is possible to also refer to both.
The molded body in the present invention, means a processed product or Supplementary type products processing or Fugata polyethylene resin composition into a suitable form depending on intended use and specifically, films, bags, sheets , coatings, fibers, yarns, containers, tubes, pipes, coatings, lids, caps, boxes, miscellaneous goods such, toys, medical instruments parts, beads, microparticles, can be exemplified foaming products, etc., these, or a multilayer structure may or a composite article with other members. These Applications of molded bodies of the polyethylene resin composition of the present invention and specifically serial example, stated standard bag dimensional standards such as inner bag or garbage bag paper bags, heavy bags, wrapping films, sugar bags, rice bag, the oil product packaging bags, films for food packaging in anhydride packaging bag, such as pickles, agricultural film such as nylon, polyester, metal foil, ethylene - laminate of various substrates, such as vinyl acetate copolymer saponification product , or used as a foam or a molded article thereof, bag-in-box, detergent containers, edible oil containers, retort containers, medical containers, chemical containers, solvent containers, pesticide containers, such as various plastics bottle products, kerosene cans, drums, hollow containers such as fuel tanks, infusion bag, various tubes, water pipes, pipes such as a gas pipe, Tupperware lid for the container, bottle caps, containers, etc., known polyether Ren resin, it is possible to see the application of the molded article of the polyethylene resin composition.

The molding method of the molded article of the present invention have excellent molding properties and mechanical properties of the polyethylene resin composition of the present invention is not particularly limited as long as it is a method capable of effectively utilizing the transparency is an example of a primarily intended upcoming applications films of polyethylene resin composition of the present invention, the bag, if the sheet, the preferred molding method, molding condition, as applications, for example, Japanese Patent 2007-197722 JP , Japanese Patent 2007-177168 discloses, Japanese Patent 2007-177187 discloses, Japanese Patent 2010-31270 Patent various inflation molding method such as is described in detail in such publications, T-die film molding Law, calender molding, be specifically mentioned multilayer film molding method, and various applications by multi-layer co-extrusion molding machine and lamination That. Of course, gas or other than air in inflation molding, liquid can be used as a refrigerant, a stretch (inflation simultaneous biaxial stretching) can also be used for special inflation molding, such as molding or multi-stage blow.

The thickness of the film product thus obtained (or sheet) is not particularly limited, is different suitable thickness by molding method and conditions. For example, in the case of inflation molding, it is about 5 ~ 300 [mu] m, in the case of T-die molding, can be about 5 [mu] m ~ 5 mm of the film (or sheet). Similarly, in the case of polyethylene hollow containers which is an example of a primarily intended upcoming applications of the resin composition of the present invention, the preferred molding method, molding condition, as applications, for example, Japanese Patent 2004-18812 JP , Japanese Patent 2009-143079 discloses, Japanese Patent 2009-173889 discloses a variety of a blow molding method, as described in detail in equal, specifically mentioned that the blow molding method, etc., and various applications can. Likewise, the pipe is an example of application of the polyethylene resin composition of the present invention, the coating material, a lid, caps, boxes, cases miscellaneous goods, the preferred molding method, molding condition, as applications, for example, Japanese Patent open 2007-2235, JP Japanese Patent 2007-177183 discloses, be mentioned specifically various molding methods and various applications, as described in detail in Japanese Patent 2002-60559 Patent Laid it can. Furthermore, as the application of the polyethylene resin composition of the present invention, other polyethylene resin, and polyethylene resin composition, and an appropriate amount blended into polyolefin resins such as polypropylene resins, and moldability improves the mechanical strength improved low-temperature resistance imparted, low-temperature adhesion-imparting, can be used as a modifier and the like.

[III] A second aspect of the ethylene polymer of the Invention The present invention is related to ethylene polymer having excellent moldability which has a long-chain branched structure developed. Hereinafter, a second aspect of the present invention will be described for each item.
Ethylene polymer of the present invention satisfies all of the conditions described below (B-1 ') ~ (B-8).

III-1. Conditions (B-1 ')
MFR B of the ethylene-based polymer in the present invention, 0.001 ~ 200 g / 10 min, preferably 0.01 ~ 100 g / 10 min, more preferably 0.05 ~ 50 g / 10 min, particularly preferably 0.1 ~ 50 g / 10 min, most preferably from 0.1 ~ 10 g / 10 min. Since MFR B is ethylene moldability of the polymer, in particular or poor melt flowability and spreadability, difficult to mix uniformly with the other resins is less than 0.001 g / 10 min, gels, fish eyes, fish overview failure or caused such eye, since the impact strength and transparency tend to decrease, such being undesirable. MFR B is undesirable impact strength of the composition mixed with 200 g / 10 min larger than the ethylene polymer and the polymer other resins, the mechanical strength such as tear strength and tensile strength decreases. Incidentally, MFR is a value when measured under the same conditions as the above conditions (A-1).

III-2. Conditions (B-2 ")
Density B of the ethylene polymer in the present invention, 0.880 ~ 0.970g / cm 3, preferably 0.891 ~ 0.960g / cm 3, more preferably 0.895 ~ 0.950g / cm 3, Tokuni the Konomashiku 0.900 ~ 0.934g / cm 3, the Mottomo Konomashiku an 0.900 ~ 0.925g / cm 3. If the density B is in this range, balance and transparency of impact strength and rigidity of the ethylene polymer and the molded product is excellent. On the other hand, the density B rigidity is lowered is less than 0.880 g / cm 3, if the product is a thin molded article having a thickness of a film or sheet or the like, various disadvantages in product use, of course, the product winding process, the surface it is not preferable because inconvenience in the process step after such printing and lamination, if the product is a thick molded article such as a pipe or various containers, for product is too soft deformation, the large thickness designed unnecessarily Sako It is not preferable because it is. You can also become difficult to handle badly stickiness even at room temperature when subjected to blending process with other resin is not preferable causing product stickiness of the resin composition, further, the said other resin compatibility is reduced, the phase impact strength and transparency by the separation is likely to deteriorate. Also, undesirable density B 0.970 g / cm 3 greater than the impact strength and transparency are impaired. When used as an intensity for enhancing modifier other resins, the density of the ethylene polymer in the present invention is preferably in the range of 0.900 ~ 0.910g / cm 3. The density refers to a value measured under the same conditions as the above conditions (A-2).

III-3. Conditions (B-3)
[Mw / Mn] B of the ethylene-based polymer in the present invention, 2.0-10.0, preferably 2.0-6.0, more preferably from 2.5 to 5.6 and more preferably 2. 9 to 4.5, and particularly preferably 3.2 to 4.0. [Mw / Mn] may decrease the molding property is B is less than 2.0, should be avoided because it may or hardly mixed with other resin. [Mw / Mn] or B becomes insufficient impact strength of the mixed resin composition and molded article of greater than 10.0 and the ethylene polymer and other resin, deteriorates transparency, easily tackiness since undesirable. Incidentally, Mw / Mn refers to a value measured under the same conditions as the above conditions (A-3).

III-4. Conditions (B-4 ')
Of ethylene polymer in the present invention [λmax (2.0)] B from 1.2 to 30.0 preferably 1.5 to 20.0 more preferably 2.0-10.0, more preferably it is 2.4 to 6.0, and particularly preferably from 3.0 to 5.0. [Λmax (2.0)] B is the ethylene polymer is less than 1.2, the fluidity and the melt tension of the mixed resin composition and molded article with other resins becomes insufficient, molding characteristics may deteriorate . And [λmax (2.0)] B is greater than 30.0, although excellent in flowability and melt tension, preferably so the impact strength may decrease, such as the ethylene polymer, the transparency or to deteriorate Absent. Incidentally, .lambda.max (2.0) refers to the value as measured under the same conditions as the above conditions (A-4). For the effect of extensional flow properties of the polyethylene it has on the mechanical properties surface of the molding processability and the molded body, is already as described in the section of the above conditions (A-4) and conditions (B-4).

III-5. Conditions (B-5)
The ethylene polymer in the present invention is defined by the condition of the above Section 2.5 (B-5) [λmax ( 2.0)] B /[λmax(0.1)] B is 1.2 to 10.0, preferably 1.3 to 5.0, and more preferably 1.4 to 4.0, more preferably 1.5 to 3.0.[Λmax (2.0)] B /[λmax(0.1 )] The ethylene polymer in B is less than 1.2, or not a uniform molten state of the mixed resin composition and molded article with other resins , or there could be a thermally unstable structure, and or cause very long long chain present in deterioration of reduction and transparency of the impact strength according to the strength anisotropy of the molded body due branched structure , which is not preferable. [Λmax (2.0)] and B /[λmax(0.1)] B is greater than 10.0, although excellent in melt tension and fluidity during molding, the ethylene polymer, mixed with other resins lowered impact strength of the resin composition and molded article is not preferable because transparency is deteriorated.

III-6. Conditions (B-6)
Ethylene polymer of the present invention is a polymer prepared by polymerization of ethylene using a catalyst containing a transition metal, is matters stated in the conditions of Section 2.6 above (B-6) It applies to all.

III-7. Conditions (B-7)
The ethylene polymer in the present invention is a g C 'is 0.30 to 0.70 above, matters described in the section of the conditions of section 2.7 of the above (B-7) is applied all. g C 'value is preferably from 0.30 to 0.59, more preferably 0.35 to 0.55, and more preferably 0.35 to 0.50 and particularly preferably 0.35 ~ is 0.45. g C 'value mixed resin composition of 0.70 is greater than the said ethylene polymer and another resin, is insufficient or moldability of a molded article, transparency unfavorably insufficient. g and C 'value of 0.30 less than the moldability such as the ethylene polymer improved, lowered impact strength of the molded body is not preferable because transparency is deteriorated. Incidentally, W C value of g C 'value and the next section, the value when measured under the same conditions as in Section 2.7 above (B-7), and Section 2.8 of the condition (B-8) the say.

III-8. Conditions (B-8)
The ethylene polymer in the present invention, the aforementioned W C is from 0.01 to 30.0% matters stated in the conditions of Section 2.8 above (B-8) is applied all. W C value is more preferably 0.02 to 10.0%, more preferably from 0.05 to 8.0%, particularly preferably 0.10 to 6.0%, most preferably is 0.11 to 4.0 percent. W C value is lower than 0.01% and the ethylene polymer, is insufficient or moldability of the mixed resin composition with another resin, the transparency of such the ethylene-based polymer or insufficient unfavorable Te. W and C value is greater than 30.0%, of the moldability such as the ethylene-based polymer, is improved in melt tension, too low melt flowability, Ya Manufacture of the ethylene-based polymer since hinder molding undesirable and even lowered impact strength of the molded body, the transparency is deteriorated unfavorably.

III-9. Conditions (B-9)
The ethylene polymer in the present invention, in addition to the conditions from III-1 described above was defined in the section III-8 (B-1 ') from the condition (B-8), further the following conditions (B-9) it is preferable to satisfy.
Condition (B-9), in a TREF measurement using o-dichlorobenzene solvent, the content of components eluted at -15(W -15; units wt%) is not more than 2.0 wt%.
W -15 value is preferably not more than 0.9 wt%, more preferably not more than 0.6 wt%, still more preferably 0.5 wt%, particularly preferably 0.4 wt%, and most preferably it is 0.3wt%. The lower limit of the W -15 value is that it is not detected, preferably 0.0 wt%. W -15 value is 2.0 wt% greater than the ethylene polymer, mixed resin composition with another resin, the impact strength may decrease of the molded article, deteriorated transparency as it may become easier tackiness preferably Absent. Also, undesirable compatibility with other resin is a worsening factor for impact strength and transparency deteriorate. W -15 value in the present invention is measured by the following method.
It was dissolved sample orthodichlorobenzene (0.5mg / mLBHT pieces) at 140 ° C. and a solution. It was cooled 100 ° C. at 8 ° C. / min cooling rate after introduction into TREF column 140 ° C., and cooled to continue -15 ° C. at 4 ° C. / min cooling rate and held 60 minutes. Thereafter, ortho-dichlorobenzene is the solvent (0.5mg / mLBHT pieces) through the column at a flow rate of 1 mL / min, the components dissolved in orthodichlorobenzene -15 ° C. in a TREF column eluted 10 minutes, then the column with heating rate of 100 ° C. / time heated linearly to 140 ° C., to obtain an elution curve.

apparatus;
(TREF section)
TREF column: 4.3mmφ × 150mm stainless steel column Column filler: 100 [mu] m surface deactivated glass beads heating system: aluminum heat block Cooling system: Peltier element (cooling of the Peltier element is water-cooling)
Temperature distribution: ± 0.5 ℃
Temperature controller: manufactured) CHINO digital program adjusting meter KP1000
(Valve oven)
Heating system: Air bath type oven at measurement temperature: 140 ° C.
Temperature distribution: ± 1 ℃
Valve: six-way valve, 4-way valve (Sample injection section)
Injection method: loop injection method Injection volume: loop size 0.1ml
Inlet heating system: aluminum heat block at measurement temperature: 140 ° C.
(Detection unit)
Detector: wavelength fixed type infrared detector FOXBORO Co. MIRAN 1A
Detection wavelength: 3.42μm
Hot flow cell: LC-IR for Micro Flow Cell, optical path length 1.5 mm, window shape 2 [phi × 4 mm length round, synthetic sapphire window plate at measurement temperature: 140 ° C.
(Pump section)
The feed pump: Senshu Scientific Co., Ltd. SSC-3461 pump measurement conditions;
Solvent: ortho-dichlorobenzene (0.5mg / mLBHT containing)
Sample concentration: 5mg / mL
Sample injection volume: 0.1mL
Solvent flow rate: 1 mL / min

[IV] A third aspect of the olefin polymerization catalyst component the invention of the present invention is useful for making a sufficient number of metallocene polyolefin or metallocene polyethylene having a long chain branch of an appropriate length, the specific those of the olefin polymerization catalyst containing the catalyst component and the component for the polymerization of olefins comprising a metallocene compound having a structure. Hereinafter, a third embodiment of the present invention will be described for each item.
Olefin polymerization catalyst component of the present invention, or an olefin polymerization catalyst component comprising the following component (A-1b) and the component (A-2b), or a catalyst for olefin polymerization comprising the following components (Ac) it is a component.

IV-1. A first aspect of an olefin polymerization catalyst component of component (A-1b) and component (A-2b) olefin polymerization catalyst component present invention comprising the present invention, the components to be subsequently defined (A-1b) and component (a-2b) comprising as essential components.
Component (A-1b): a metallocene compound represented by the following general formula (1b)

Figure JPOXMLDOC01-appb-C000033

Wherein (1b), M 1b represents any of the transition metals Ti, Zr or Hf. X 1b and X 2b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1b and Q 2b are each independently a carbon atom, a silicon atom or a germanium atom. R 1b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four at least two bonded out of R 1b, to form a ring together with Q 1b and Q 2b it may be. m b is 0 or 1, if m b is 0, Q 1b is directly bonded to the conjugated 5-membered ring containing R 2b and R 3b. R 2b, R 3b and R 4b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 2b, of R 3b and R 4b, or one pair of adjacent R 3b each other or adjacent R 2b and R 3b only may form a ring together with the carbon atom bonded. ]

Component (A-2b): a metallocene compound represented by the following general formula (2b)

Figure JPOXMLDOC01-appb-C000034

Wherein (2b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other. R 12b, R 14b and R 15b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, indicates an atom or group selected from halogen-containing hydrocarbon group, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom having 1 to 20 carbon atoms but of them, at least not one hydrogen atom. R 13b are each independently a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom. R 12b, R 13b, of R 14b and R 15b, between the adjacent R 12b, either one pair of adjacent R 13b together or adjacent R 12b and R 13b only, adjacent R 14b together, adjacent R 15b or between any one pair of adjacent R 14b and R 15b only, they may form a ring together with the bond to which carbon atoms. ]

Hereinafter, the above components (A-1b) and (A-2b) (hereinafter collectively both component (Ab) or may be simply referred to as Ab.) Will be described in detail.

IV-1 (1). Component (A-1b)
The olefin polymerization catalyst component of the present invention is characterized in that comprises a metallocene compound represented by the general formula as component (A-1b) (1b).
In the general formula (1b), M 1b of the metallocene compounds, Ti, represents Zr or Hf, preferably an Zr or Hf, and more preferably a Zr.
Further, X 1b and X 2b are, specifically, a hydrogen atom or a chlorine atom, a bromine atom, an iodine atom or a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxymethyl group, ethoxymethyl group, n- propoxymethyl group, i- propoxymethyl, n- butoxymethyl group, i- butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, an acetyl group, 1-oxopropyl group, 1-oxo -n- butyl group, 2- methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo - propyl group, a phenyl acetyl group, diphenylacetyl groups, Ben Yl group, 2-methoxyphenyl group, 3-methoxyphenyl group, a 4-methoxyphenyl group, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-i- propyl aminomethyl group, bis (dimethylamino) methyl group, bis (di-i- propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methylimino group, ethylimino group, 1- (methylimino) ethyl group, 1- (phenylimino) ethyl , 1 - [(phenylmethyl) imino] ethyl group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, t-butoxy group, a phenoxy group, dimethylamino group, diethylamino group , di-n- propylamino group, di-i- propylamino group, di-n- butylamino group, di i- Butylamino group, di-t- butylamino group, and a diphenylamino group.
Specific examples of preferred X 1b and X 2b, a chlorine atom, a bromine atom, a methyl group, n- butyl group, i- butyl group, a methoxy group, an ethoxy group, i- propoxy, n- butoxy group, a phenoxy group, dimethylamino group, di-i- propylamino group. Among these specific examples, a chlorine atom, a methyl group, a dimethylamino group is particularly preferred.

Also, Q 1b and Q 2b are each independently represent a carbon atom, a silicon atom or germanium atom, preferably a carbon atom or a silicon atom.
Furthermore, as the R 1b, independently, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , neopentyl group, cyclopentyl group, n- hexyl group, a cyclohexyl group, and a phenyl group. Further, as a case of forming a ring together with Q 1b and Q 2b and at least two members out of R 1b, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group cyclohexylene, sila cyclobutyl group, Sila cyclopentyl group and silacyclohexyl groups.
Specific examples of preferred R 1b, when Q 1b or / and Q 2b is a carbon atom, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, include cyclobutylidene group, also, Q 1b or / and Q 2b If it is a silicon atom, a methyl group, an ethyl group, a phenyl group, and silacyclooctane butyl group.

Also, R 2b, R 3b and R 4b, specifically, a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methyl phenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group , 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3 , 4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t- butylsilyl group, di-t- butyl methyl silyl group, t- butyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) such Shirirufuriru group.
Further, among R 2b, R 3b and R 4b, any one or more hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6, carbon atoms halogen-containing hydrocarbon group having 1 to 20, if it is a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, particularly polymerization activity becomes higher, preferably .
R 2b, preferred specific examples of R 3b and R 4b is a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl radical, n - hexyl group, a cyclohexyl group, a phenyl group, 2-methyl-furyl group, and a trimethylsilyl group. Among these specific examples, a hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, more preferably a trimethylsilyl group, a hydrogen atom, a methyl group, t- butyl group, a phenyl group is particularly preferred.

Specific examples of the condensed cyclopentadienyl structure formed from two adjacent cyclopentadienyl moiety and both R 3b where R 3b is attached, include the following partial structure (I) ~ (VI) it is, the same applies to specific examples of the condensed cyclopentadienyl structure formed from adjacent R 3b and R 2b cyclopentadienyl moiety is attached and the R 3b and the R 2b.
Among these specific examples, (I), (III), (VI) are preferred. Also, on these partial structures (I) ~ (VI), R 4b may be substituted.

Figure JPOXMLDOC01-appb-C000035

Further, in the general formula (1b), m b is 0 or 1, if m b is 0, Q 1b is directly bonded to the conjugated 5-membered ring containing R 2b and R 3b.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-1b) is preferably represented by the following general formula (3b).

Figure JPOXMLDOC01-appb-C000036

Wherein (3b), M 1b represents any of the transition metals Ti, Zr or Hf. X 1b and X 2b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1b and Q 2b are each independently a carbon atom, a silicon atom or a germanium atom. R 1b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four at least two bonded out of R 1b, to form a ring together with Q 1b and Q 2b it may be. m b is 0 or 1, if m b is 0, Q 1b is directly bonded to the conjugated 5-membered ring containing R 2b and R 3b. R 2b, R 3b and R 4b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 2b, of R 3b and R 4b, or one pair of adjacent R 3b each other or adjacent R 2b and R 3b only may form a ring together with the carbon atom bonded. ]

In the general formula (3b), M 1b, X 1b, X 2b, Q 1b, Q 2b, R 1b, R 2b, R 3b, detailed definitions of R 4b, ahead of the general formula described in (1b) it is in accordance with the definition.

In the general formula (3b), particularly when R 3b is a hydrogen atom, it is preferred that R 2b is hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, while the hydrogen atoms of the two R 4b , and the remaining one is a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms , preferably oxygen an atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom, specifically, the remaining one of R 4b hydrogen atom , methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group , phenyl , Benzyl group, 2-methylphenyl group, 3-methylphenyl group, a 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo cyclopentyl, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2 , 3,4,5,6 pentafluorophenyl group, 4-trifluoromethylphenyl group, furyl , Tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) such Shirirufuriru group preferably include, more preferably R 2b is hydrogen atom, one of the two R 4 a hydrogen atom There, the remaining one is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, more preferably a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, specifically, the remaining one of R 4b are hydrogen atoms, methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- Butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, a 4-methylphenyl group, 3,5 dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group, trimethylsilyl group, tri t-butylsilyl , di t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, such as phenyl dimethylsilyl group and the like more preferably, more preferably, the remaining one of R 4b specific thereof include a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl , I- butyl, t- butyl group, a phenyl group, a trimethylsilyl group, a triphenylsilyl group, particularly preferably, in the remaining one of R 4b Specifically, a hydrogen atom, n- butyl group, i- butyl group, t- butyl group, a phenyl group, a trimethylsilyl group, a triphenylsilyl group.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-1b) is more preferably one represented by the following general formula (4b).

Figure JPOXMLDOC01-appb-C000037

Wherein (4b), M 1b represents any of the transition metals Ti, Zr or Hf. X 1b and X 2b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1b and Q 2b are each independently a carbon atom, a silicon atom or a germanium atom. R 1b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four at least two bonded out of R 1b, to form a ring together with Q 1b and Q 2b it may be. m b is 0 or 1, if m b is 0, Q 1b is R 2b, directly bonded to the conjugated 5-membered ring containing R 5b and R 6b. R 2b and R 4b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1 to 6 having 1 to 20 carbon atoms, 1 to 4 carbon atoms halogen-containing hydrocarbon group having to 20, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 4b do not form a ring together with the bond to which carbon atoms. R 5b represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 6b is an atom or group bonded to the carbon atoms of R 5b, independently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 1 containing silicon atoms 1-6 ~ 18 silicon-containing hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing a sulfur atom show. n b represents an integer of 0 to 10, if n b is 2 or more, at least two R 6b may form a ring together with the bond to which carbon atoms. ]

In the general formula (4b), M 1b, X 1b, X 2b, Q 1b, Q 2b, R 1b, R 2b, detailed definitions of R 4b, subject to the definition of the description of the previous general formula (1b) it is. Specific examples of the condensed cyclopentadienyl structure formed from a cyclopentadienyl moiety and R 5b which R 5b is bonded include the above-described partial structure (I) ~ (VI). Among these specific examples, (I), (III), (VI) are preferred. Also, on these partial structures (I) ~ (VI), R 6b may be substituted.

R 6b substituent is in other than a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-t-butyl phenyl group, 3,5-dimethylphenyl group, 3,5-di -t- butyl phenyl group, a naphthyl group, anthracenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl Group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2 , 3,4,5,6 pentafluorophenyl group, 2,6-dichloro-4-trimethylsilyl phenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenylsilyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) such Shirirufuriru group. R 6b, together with the bond to which carbon atoms may form a ring. In the general formula (4b), particularly when R 2b is a hydrogen atom, or two R 4b and R 6b are all hydrogen atom, or one of the two R 4b and R 6b at least one carbon hydrocarbon group having 1 to 20 silicon-containing hydrocarbon group having silicon atoms 1-1 carbon atoms containing from 6 to 18 1 carbon atoms containing a halogen-containing hydrocarbon group, an oxygen atom or a sulfur atom having 1 to 20 carbon atoms preferably ~ 40 hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms, specifically a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl , 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group, bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclopentyl group, 2-bromo - 3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4 - trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, trimethyl Silyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru group and the like. Further, another preferred embodiment when R 2b in the formula (4b) is a hydrogen atom, one of the two R 4b is a hydrogen atom, the remaining one is a hydrocarbon having 1 to 20 carbon atoms group, a silicon-containing hydrocarbon group having silicon atoms 1-1 carbon atoms containing from 6 to 18 halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or preferably a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms, specifically, the remaining one of R 4b are methyl, ethyl, n- propyl, i- propyl, n- butyl group , i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, - methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl , bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3- iodo cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-tri trifluoromethylphenyl group, a furyl group, tetrahydrofuryl group, 2-methyl-furyl group, Torimechirushi Group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, such as 2- (trimethyl) Shirirufuriru groups are suitably mentioned, is one of the two R 4b is a hydrogen atom, a hydrocarbon group of the remaining one is from 1 to 20 carbon atoms, silicon atoms 1-6 more preferably a silicon-containing hydrocarbon group having 1 to 18 carbon atoms including, specifically, the remaining one of R 4b are methyl, ethyl, n- propyl, i- propyl, n- butyl, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, benzyl Group, 2-methylphenyl group, 3-methylphenyl group, a 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis ( trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group, trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, is like is more preferably phenyl dimethylsilyl group, more preferably, in the remaining one of R 4b Specifically, methyl group, ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, a phenyl group, a trimethylsilyl group, a triphenylsilyl group, and particularly preferably, the remaining one of R4b is specifically, n- butyl, i- butyl, t- butyl group, a phenyl group, a trimethylsilyl group, a triphenylsilyl group. In the general formula (4b), particularly when R 4b is a hydrogen atom, R 2b and R 6b represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, having a carbon number of 1 to containing silicon atoms 1-6 18 any silicon-containing hydrocarbon group, a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a halogen-containing hydrocarbon group, an oxygen atom or a sulfur atom having 1 to 20 carbon atoms in it is the preferred, specifically either, R 2b and R 6b represents a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3, - dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3 dibromo cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t- butylsilyl Group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) any such Shirirufuriru groups are suitably exemplified, R 2b and R 6b represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 more preferably in, specifically, R 2b and R 6b represents a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group , n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylcarbamoyl Butylphenyl group, a 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethyl silyl) methyl group, trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, such as phenyl dimethylsilyl group and the like more preferably , more preferably, in the R 2b and R 6b Specifically, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, phenyl group, a trimethylsilyl group, a triphenylsilyl group, and particularly preferably, R 2b and R 6b is specifically hydrogen atoms Child, n- butyl group, i- butyl, t- butyl group, a phenyl group, a trimethylsilyl group, a triphenylsilyl group.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-1b) are those still more preferably represented by the following general formula (5b).

Figure JPOXMLDOC01-appb-C000038

Wherein (5b), M 1b represents any of the transition metals Ti, Zr or Hf. X 1b and X 2b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1b shows a carbon atom, a silicon atom or a germanium atom. R 1b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 1b may form a ring together with Q 1b coupled to each other. R 2b, R 4b and R 6b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 4b do not form a ring together with the bond to which carbon atoms. R 6b, together with the bond to which carbon atoms may form a ring. ]

In the general formula (5b), M 1b, X 1b, X 2b, Q 1b, R 1b, R 2b, R 4b, detailed definitions of R 6b, which according to the definition of the foregoing description of the general formula (4b) it is. Also, R 6b substituent is preferably a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , neopentyl group, cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-t-butylphenyl group, 3,5 - dimethylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) methyl group, trimethylsilyl group, tri t-butylsilyl group, di-t-butylmethylsilyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, a furyl group, Tet Rahidorofuriru group, 2-methyl-furyl group, a 2- (trimethyl) Shirirufuriru group, more preferably a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, more preferably a hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, a trimethylsilyl group, a hydrogen atom , methyl, t- butyl group, a phenyl group is particularly preferred. Further, in the case of forming a ring together with the carbon atom to which the substituent R 6b are attached, adjacent two R 6b forms a six-membered ring structure together with the carbon atom bonded that preferably, 4-position and more preferably to form a six-membered ring structure 5 position of both R 6b are bonded to, it is more preferable to form a benzindenyl ring structure as a whole together with indenyl ring bonded.

In the olefin polymerization catalyst component of the present invention, specific examples of the metallocene compound of the component of the olefin polymerization catalyst component (A-1b) below, not limited thereto. Incidentally, the number indicating the position of the cyclopentadienyl ring, the substituents on the indenyl ring and azulenyl ring of the metallocene compounds shown in Examples of the component (A-1b) and below (A-2b), as follows it is.

Figure JPOXMLDOC01-appb-C000039

(I) as being classified as crosslinking Cp (Ind) Zr type include metallocene compounds shown in the following Table b-1.

Figure JPOXMLDOC01-appb-T000040

(Ii) as being classified as crosslinking Cp (3- substituted Ind) Zr type include metallocene compounds shown in the following Table b-2 and Table b-3.

Figure JPOXMLDOC01-appb-T000041

Figure JPOXMLDOC01-appb-T000042

(Iii) as a crosslinking (3-substituted Cp) (Ind) those classified into Zr type include metallocene compounds shown in the following Table b-4.

Figure JPOXMLDOC01-appb-T000043

(Iv) crosslinked (4-substituted Cp) as being classified into (3-substituted Ind) Zr type include the metallocene compounds shown in the following Table b-5.

Figure JPOXMLDOC01-appb-T000044

(V) as those classified as bridged bis CpZr type include metallocene compounds shown below in Table b-6.

Figure JPOXMLDOC01-appb-T000045

(Vi) crosslinking Cp as being classified into (3-substituted Cp) Zr type include the metallocene compounds shown in the following Table b-7.

Figure JPOXMLDOC01-appb-T000046

As being classified into (vii) bridged bis (3-substituted Cp) Zr type include metallocene compounds shown in the following Table b-8.

Figure JPOXMLDOC01-appb-T000047

Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like.
Further, when the use of these metallocene compounds as the component (A-1b), it is also possible to use two or more kinds.

In the inside of the specific compounds illustrated above, "B metallocene compound as the component (A-1b), the" A "preferred from the viewpoint of excellent both polymerization activity and formability, it more preferred "and denoted by" C "in the more preferred.

Synthesis examples of the metallocene compound is a component according to the present invention (A-1b) are shown below, in these synthetic methods is not particularly limited.
For example, after the lithiated indene compound, is reacted with dichlorosilane compound, followed ligand by reaction with cyclopentadienyl lithium is obtained. The resulting ligand tetrakis (alkyl amide) zirconium, followed method is reacted with trimethylsilyl chloride and or a lithiated The resulting ligand, followed by and a method of reacting with zirconium tetrachloride.

IV-1 (2). Component (A-2b)
The olefin polymerization catalyst component of the present invention is characterized in that comprises a metallocene compound represented by the general formula as component (A-2b) (2b).
In the general formula (2b), M 2b of the metallocene compounds, Ti, represents Zr or Hf, preferably an Zr or Hf, and more preferably a Zr.
Further, X 11b and X 12b, specifically, a hydrogen atom or a chlorine atom, a bromine atom, an iodine atom or a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxymethyl group, ethoxymethyl group, n- propoxymethyl group, i- propoxymethyl, n- butoxymethyl group, i- butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, an acetyl group, 1-oxopropyl group, 1-oxo -n- butyl group, 2- methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo - propyl group, a phenyl acetyl group, diphenylacetyl groups, Nzoiru group, 2-methoxyphenyl group, 3-methoxyphenyl group, a 4-methoxyphenyl group, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-i- propyl aminomethyl group, bis (dimethylamino) methyl group, bis (di-i- propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methylimino group, ethylimino group, 1- (methylimino) ethyl group, 1- (phenylimino) ethyl , 1 - [(phenylmethyl) imino] ethyl group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, t-butoxy group, a phenoxy group, dimethylamino group, diethylamino group , di-n- propylamino group, di-i- propylamino group, di-n- butylamino group, di i- butylamino group, di-t- butylamino group, and a diphenylamino group.
Specific examples of preferred X 11b and X 12b, each independently, a chlorine atom, a bromine atom, a methyl group, n- butyl group, i- butyl group, a methoxy group, an ethoxy group, i- propoxy, n- butoxy group, a phenoxy group, dimethylamino group, di-i- propylamino group. Among these specific examples, a chlorine atom, a methyl group, a dimethylamino group is particularly preferred.

Also, Q 11b represents a carbon atom, a silicon atom or germanium atom, preferably a carbon atom or a silicon atom.
Furthermore, as the R 11b, each independently, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , neopentyl group, cyclopentyl group, n- hexyl group, a cyclohexyl group, and a phenyl group. Further, as a case where R 11b form a ring together with Q 11b, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group cyclohexylene, sila cyclobutyl group, silacyclopentyl groups, and silacyclohexyl groups .
Specific examples of preferred R 11b, when Q 11b is a carbon atom, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, include cyclobutylidene group, and when Q 11b is a silicon atom, a methyl group, ethyl group, a phenyl group, and silacyclooctane butyl group.

R 12b, R 14b and R 15b are each specifically hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methyl phenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentanol Butyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2 , 3,4,5,6 pentafluorophenyl group, 4-trifluoromethylphenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, a triphenylsilyl group , diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru including but element or group selected from group. of these, at least one One is not a hydrogen atom, preferably, each specifically, hydrogen atoms , Methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group , furyl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru although element or group chosen from groups include, among them, at least one is not hydrogen atom, more preferably, each specific the hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, a trimethylsilyl group, 2-methyl-furyl group, 2-including but element or group selected from (trimethyl) Shirirufuriru group, of these, that at least one hydrogen atom, the are preferably not hydrogen atoms, R 1 is located at the 2-position on the cyclopentadienyl ring It is at least one of R 14b and two R 15b located b the same 2-position, the and more preferably not a hydrogen atom, a R 12b is located at the 2-position on the cyclopentadienyl ring 2 one of is at least one of R 15b, the it is more preferably not hydrogen atoms at least one of R 15b located R 12b and the 2-position which is located at the 2-position on the cyclopentadienyl ring One is is.

R 13b is specifically each independently a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, a 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t- butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group , 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3 - iodo cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4- trifluoromethylphenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenyl silyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru group and the like, preferably, each independently, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, n- hexyl group, cyclohexyl , A phenyl group, a trimethylsilyl group, a furyl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru group, more preferably each independently a methyl group, n- butyl group, t- butyl group, a phenyl group, a trimethylsilyl group, 2-methyl-furyl group, 2-include element or group selected from (trimethyl) Shirirufuriru group.

In the general formula (2b), R 12b adjacent to each other are bonded to are cyclopentadienyl rings on ingredients together with the carbon atom (A-1b) moiety shown in the description of (I) ~ (VI condensed cyclopentadienyl structure), preferably (I), (III), it may also form a condensed ring cyclopentadienyl structure (VI), this time, the adjacent R 13b and between the adjacent between R 12b and R 13b that, the ring structure is not formed. Similarly, formed between the adjacent R 13b is condensed cyclopentadienyl structure of the (I) ~ (VI), preferably at (I), (III), condensed cyclopentadienyl structure (VI) may also be, at this time, between the adjacent R 12b and between the adjacent R 12b and R 13b, the ring structure is not formed. More Similarly, condensed cyclopentadienyl structure of the same between adjacent R 12b and R 13b (I) ~ (VI ), preferably (I), (III), condensed-ring (VI) Shikuropentaji it may form a enyl structure, but this time, in the adjacent R 12b and between the adjacent R 13b together, the ring structure is not formed.

In the general formula (2b), condensed cyclopentadienyl structure between the adjacent R 14b are the same (I) ~ (VI), preferably (I), (III), condensed-ring (VI) may form a cyclopentadienyl structure, but this time, between the adjacent R 15b and between the adjacent R 14b and R 15b, the ring structure is not formed. Similarly, formed between the adjacent R 15b is condensed cyclopentadienyl structure of the (I) ~ (VI), preferably at (I), (III), condensed cyclopentadienyl structure (VI) may also be, at this time, between the adjacent R 14b and between the adjacent R 14b and R 15b, the ring structure is not formed. More Similarly, condensed cyclopentadienyl structure of the same between adjacent R 14b and R 15b (I) ~ (VI ), preferably (I), (III), condensed-ring (VI) Shikuropentaji it may form a enyl structure, but this time, in the adjacent R 14b and between the adjacent R 15b together, the ring structure is not formed.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-2b) is preferably one represented by the following general formula (6b).

Figure JPOXMLDOC01-appb-C000048

Wherein (6b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other. R 12b and R 14b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1 to 6 having 1 to 20 carbon atoms, 1 to 4 carbon atoms halogen-containing hydrocarbon group having to 20, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 12b and R 14b do not form a ring together with the bond to which carbon atoms. R 16b and R 17b each independently represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 18b and R 19b are each an atom or group bonded to the carbon atoms of R 16b or R 17b, each independently, a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, silicon atoms 1 silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing 6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, oxygen atoms or 1 to 40 carbon atoms containing a sulfur atom hydrocarbon group or having 1 to 40 carbon atoms a hydrocarbon group-substituted silyl group. p b and q b are each independently 0 to an integer of 10, when p b and q b is 2 or more, two each of at least of R 18b and R 19b are joined to that carbon atom it may form a ring together with. ]

In the general formula (6b), M 2b, X 11b, X 12b, detailed definitions of Q 11b and R 11b, is in accordance with the definition of the foregoing description of the general formula (2b).

In the general formula (6b), R 12b and R 14b are each specifically hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl group, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3- methylphenyl group, a 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyl dimethylsilyl) methyl group, bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl , 2-bromo-cyclopentyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4 chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenylsilyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru element or group selected from group and the like, preferably, each specifically hydrogen atom, methyl group, ethyl group, n- flop Propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group, a furyl group, 2-methyl-furyl group , 2- (trimethyl) include element or group chosen from Shirirufuriru group, more preferably, each specifically hydrogen atom, methyl group, n- butyl group, t- butyl group, a phenyl group, trimethylsilyl group, 2-methyl-furyl group, and an element or a group selected from 2- (trimethyl) Shirirufuriru group. Further, at least one of R 14b located R 12b and the 2-position which is located at the 2-position on the cyclopentadienyl ring, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group, a furyl group, 2-methyl-furyl group, selected from 2- (trimethyl) Shirirufuriru group more preferable to be that group, particularly preferably a methyl group, n- butyl group, t- butyl group, a phenyl group, a trimethylsilyl group, 2-methyl-furyl group, a group selected from 2- (trimethyl) Shirirufuriru group .
Specific examples of the condensed cyclopentadienyl structure formed from a cyclopentadienyl moiety and R 16b where R 16b is bonded include the above-described partial structure (I) ~ (VI). Among these specific examples, (I), (III), (VI) are preferred. Also, on these partial structures (I) ~ (VI), R 18b may be substituted.

R 18b substituents, in addition to a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-t-butyl phenyl group, 3,5-dimethylphenyl group, 3,5-di -t- butyl phenyl group, a naphthyl group, anthracenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentanol Butyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2 , 3,4,5,6 pentafluorophenyl group, 2,6-dichloro-4-trimethylsilyl phenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenylsilyl group, diphenylmethyl silyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) such Shirirufuriru group. R 18b, together with the bond to which carbon atoms may form a ring.

In the general formula (6b), R 17b and R 19b are also defined in the same manner as R 16b and R 18b independently.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-2b) are preferred those represented by the following general formula (7b).

Figure JPOXMLDOC01-appb-C000049

Wherein (7b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other. R 12b, R 14b and R 15b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, indicates an atom or group selected from halogen-containing hydrocarbon group, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom having 1 to 20 carbon atoms but among them, is located at the 2-position and 5-position on both the cyclopentadienyl rings. R 12b, of R 14b and R 15b, at least not one hydrogen atom.R12b, R 14b, R 15b do not form a ring together with the bond to which carbon atoms. R 16b represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 18b is an atom or group bonded to the carbon atoms of R 16b, each independently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 1 containing silicon atoms 1-6 ~ 18 silicon-containing hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom or a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom show. p b is an integer of 0 to 10, if p b is 2 or more, at least two R 18b, together with binding to that carbon atom may form a ring. ]

Detailed definitions of the above in the general formula (7b), M 2b, X 11b, X 12b, Q 11b, R 11b, R 16b and R 18b are in accordance with the definition of the foregoing description of the general formula (6b).

Similarly, the general formula (7b), R 12b, R 14b and R 15b are each specifically hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a 2-methylphenyl group , 3-methylphenyl group, a 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis ( t- butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3- Bro Mopuropiru group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl-dimethyl-silyl group, triphenylsilyl group, diphenylmethylsilyl group, a phenyl dimethylsilyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, 2- (trimethyl) Shirirufuriru including but element or group selected from group, among them, Oyo 2-position on both the cyclopentadienyl ringR 12b located at the 5-position, R 14b, of R 15b, that at least one hydrogen atom, preferably, each specifically hydrogen atom, methyl group, ethyl group, n- propyl group, i - propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group, a furyl group, 2-methyl-furyl group, 2- ( including but element or group selected from trimethyl) Shirirufuriru group, among them, R 12b is located at the 2-position and 5-position on both cyclopentadienyl ring, R 14b, of R 15b, at least one is not hydrogen atom, more preferably, each specifically hydrogen atom, methyl group, n- butyl group, t- butyl group, a phenyl group, a trimethylsilyl group, 2- Chirufuriru group, 2- (trimethyl) Shirirufuriru although element or group chosen from groups include, among them, R 12b is located at the 2-position and 5-position on both cyclopentadienyl ring, R 14b, R 15b of, at least not one hydrogen atom. In the general formula (7b), R 12b is located at the 2-position on the cyclopentadienyl rings is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing carbide having 1 to 18 carbon atoms containing silicon atoms 1-6 hydrogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, atoms selected from hydrocarbyl-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom, or more preferable to be a group, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group , a phenyl group, a trimethylsilyl group, a furyl group, 2-methyl-furyl group, particularly preferably a group selected from 2- (trimethyl) Shirirufuriru group, a methyl group, n- butyl group, t- butyl group, Phenyl group, a trimethylsilyl group, 2-methyl-furyl group, most preferably a group selected from 2- (trimethyl) Shirirufuriru group. In the general formula (7b), R 12b, R 14b, R 15b do not form a ring together with the bond to which carbon atoms.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-2b) is more preferably one represented by the following general formula (8b).

Figure JPOXMLDOC01-appb-C000050

Wherein (8b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other.R12b, R 14b, R 18b and R 19b are each independently hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing carbide having 1 to 18 carbon atoms containing silicon atoms 1-6 hydrogen group, a halogen-containing hydrocarbon group, an oxygen atom or a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom having 1 to 20 carbon atoms. R 12b and R 14b do not form a ring together with the bond to which carbon atoms. R 18b and R 19b, together with the bond to which carbon atoms may form a ring. ]

In the general formula (8b), M 2b, X 11b, X 12b, Q 11b, R 11b, R 12b, R 14b, detailed definitions of R 18b and R 19b, the preceding general formula (6b) Description it is in accordance with the definition.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-2b) are those also more preferably represented by the following general formula (9b).

Figure JPOXMLDOC01-appb-C000051

Wherein (9b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other. R 12b, R 14b and R 15b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, indicates an atom or group selected from halogen-containing hydrocarbon group, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom having 1 to 20 carbon atoms but among them, of R 14b and R 15b are located at the 2-position and 5-position on R 12b and cyclopentadienyl rings located at the 2-position on the indenyl ring, at least not one hydrogen atom. R 12b, R 14b and R 15b do not form a ring together with the bond to which carbon atoms. R 18b, together with the bond to which carbon atoms may form a ring. ]

In the general formula (9b), M 2b, X 11b, X 12b, Q 11b, R 11b, R 12b, R 14b, detailed definitions of R 15b and R 18b, the preceding general formula (6b) Description it is in accordance with the definition.

As an olefin polymerization catalyst component according to the present invention, the metallocene compound of the component (A-2b), the above general formula (2b), the general formula (6b) ~ of either the indicated are those (9b), its conjugate 5 2-position of the R 12b is a substituent on-membered ring, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group having 6 to 12 carbon atoms, 1-2 carbon atoms 8 having an alkenyl group, a halogen-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, an alkyl group with a trialkylsilyl group having 1 to 3 carbon atoms an alkyl group having 1 to 3 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms or oxygen-containing heterocyclic group, and are preferred sulfur-containing heterocyclic group. The substituent R 12b of such preferred second place, specifically, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group , chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group , 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3 , 4,5,6-pentafluorophenyl group, a 4-trifluoromethylphenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, a triphenylsilyl group, diphenyl methylsilyl group, and a phenyl dimethylsilyl group and the like, more preferably, specifically, methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, trimethylsilyl group ani Is, more preferably, specifically, methyl group, n- butyl group, t- butyl group, a phenyl group and a trimethylsilyl group.

Moreover, it can be mentioned as examples of another specific chemical structures of the preferred 2-position substituent R 12b, oxygen-containing heterocyclic group having a structure represented by the following general formula (10b), a sulfur-containing heterocyclic group.

Figure JPOXMLDOC01-appb-C000052

In the general formula (10b), R 21b and R 22b are each same as may be the or different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon atoms alkenyl group of 2 to 8, halogen-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, the alkyl group is trialkylsilyl having 1 to 3 carbon atoms alkyl group having 1 to 3 carbon atoms having a group, or a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, also may constitute 6-7 membered ring both R 21b and R 22b, 6-7 membered ring may contain an unsaturated bond.

Here, specific examples of the alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, s- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
Specific examples of the alkoxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, t-butoxy group, a phenoxy group, etc. it can be mentioned. As the halogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom can be exemplified, and as specific examples of the alkenyl group having 2 to 8 carbon atoms, a vinyl group, propenyl group, allyl group, butenyl group, and a cyclohexenyl group. Furthermore, as the halogen atom of the halogen-containing alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a halogen-containing alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms are those halogen atom to a hydrogen atom on the backbone of the alkyl group is substituted, and specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tri bromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1,1- tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 5-chloropentyl, 5, 5,5-trichloro-pentyl, 5-fluoro-pentyl, 5,5,5- Ruoropenchiru, 6-chloro-hexyl, 6,6,6-trichloro-hexyl, 6-fluoro-hexyl, the 6,6,6-trifluoro-hexyl. Further, the aryl group having 6 to 18 carbon atoms, may be substituted hydrocarbon group having 1 to 6 carbon atoms, specific examples include phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, t- butylphenyl, biphenyl, 1-naphthyl, 2-naphthyl, it may be mentioned acenaphthyl, phenanthryl, anthryl and the like. Further, the specific examples of the halogen-containing aryl group having 6 to 18 carbon atoms, a hydrogen atom of the aryl group of the carbon number of 6 to 18 are those obtained by replacing the halogen atom, specifically, 2-, 3 -, each fluorophenyl 4-substituted, 2-, 3-, 4- respective chlorophenyl substituent, 2-, 3-, each of 4-substituted bromophenyl, 2,4-, 2,5-, 2,6 -, each difluorophenyl 3,5-substituted, 2,4, 2,5, 2,6, 3,5 each dichlorophenyl substituted, 2,4,6, 2,3,4, 2,4,5, each trifluorophenyl 3,4,5-substituted, 2,4,6, 2,3,4, 2,4,5, 3,4,5-substituted each trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 3,5-dimethyl-4-chlorophenyl, 3,5-dichloro Such as 4-biphenyl, and the like. The number 1 and the 1-3 alkyl group, carbon number trialkylsilyl groups having different carbon atoms and optionally 1 to 3 alkyl group with a carbon having an alkyl group is a trialkylsilyl group having 1 to 3 carbon atoms it is those which are substituted with hydrogen atoms on the alkyl group of 1 to 3, and specific examples thereof include trimethylsilyl methyl, trimethylsilylethyl. Further, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, a substituent three hydrocarbon groups different optionally 1 carbon atoms which may be 1-6 is substituted on silicon, carbon 1 the hydrocarbons to 6, the above-described alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a halogen-containing alkyl group and a phenyl group having 1 to 6 carbon atoms include, may have a substituent on the phenyl group include trimethylsilyl, triethylsilyl, tri -n- butylsilyl, t- butyl dimethyl silyl, trivinylsilyl, triallyl silyl, triphenyl silyl it can be mentioned.

As R 21b and R 22b, each independently, silyl preferably having a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a hydrocarbon group having 1 to 6 carbon atoms of 6 to 18 carbon atoms a group. If R 21b is a hydrogen atom, synthesis yield is low, R 21b is a substituent other than a hydrogen atom is preferred. R 21b is more preferably a silyl group having an alkyl group, an aryl group or a hydrocarbon group having 1 to 6 carbon atoms of 6 to 18 carbon atoms having 1 to 6 carbon atoms. R 22b is more preferably an alkyl group having 1 to 6 several hydrogen atoms or carbon. Specific preferred substituents, R 21b is methyl, ethyl, t- butyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group, a triphenylsilyl group, R 22b is a hydrogen atom, a methyl group, an ethyl group it is.
R 21b and R 22b may constitute a 6-7 membered ring with both 6-7 membered ring may contain an unsaturated bond. Specific substitutions, as 2-position substituent of the indene ring include benzofuryl group, a benzothienyl group.

In the olefin polymerization catalyst component of the present invention, specific examples of the metallocene compound of the component of the olefin polymerization catalyst component (A-2b) below, not limited thereto.
(I) such as or a crosslinking Cp 2 Zr type classified by metallocene compound, Japanese Patent Laid-Open 2-76887 discloses, Japanese Patent Laid-Open 3-12406 discloses, Japanese Patent Laid-Open 3-12407, JP-Japanese Patent No. 3-12407, JP-Japanese Patent Laid-Open 11-315089 and JP Japanese Patent 2009-143901 discloses, Japanese Kohyo 2005-507961 discloses, etc., among some of the described supra literature, the general bridged bis (alkyl substituted cyclopentadienyl) zirconium compounds belonging to formula (2b), the general formula (2b) to be described belong Japanese Kohyo 2002-535339 Patent Laid the oxygen-containing hydrocarbon group, a sulfur-containing hydrocarbon among the zirconium compound having a hydrogen group, a cyclopentadienyl ring substituted with a hydrocarbon group-substituted silyl group or the like, belonging to the general formula (2b) Bridged bis (alkyl substituted cyclopentadienyl) zirconium compounds that, and the like.
The metallocene compounds classified into crosslinking Cp 2 Zr type shown in Table b-9 and Table b-10.

Figure JPOXMLDOC01-appb-T000053

Figure JPOXMLDOC01-appb-T000054

(Ii) or metallocene compounds classified as crosslinked Ind 2 Zr type, Japanese Patent Laid-Open 8-59724 discloses, Japanese Patent Laid-Open 10-231314 and JP Japanese Patent 2003-105029, JP-Japanese Patent open 2004-352707, JP-like, among some of the described supra literature, the general formula (6b), belonging bridged bis general formula (8b) (substituted or unsubstituted indenyl) zirconium compounds, bridged bis (substituted or unsubstituted substituted azulenyl) zirconium compounds, cross-linking (substituted or unsubstituted indenyl) (or a substituted or unsubstituted azulenyl) zirconium compounds, Japanese Kohyo 2002-535339 discloses, Japanese Patent 2004-352707 discloses, etc., to the foregoing literature among some of the described, the general formula (6b), oxygenated hydrocarbons belonging to general formula (8b) , Sulfur-containing hydrocarbon group, a zirconium compound having a hydrocarbon group-substituted silyl group the indenyl ring or azulenyl ring substituted with etc., and the like.
The metallocene compounds classified into crosslinked Ind 2 Zr type shown in Table b-11 and Table b-12.

Figure JPOXMLDOC01-appb-T000055

Figure JPOXMLDOC01-appb-T000056

Or (iii) a metallocene compound or the like classified into crosslinked CpIndZr type, Japanese Patent Laid-Open 6-87922 discloses, Japanese Patent Laid-Open 8-92308 discloses, Japanese Patent Laid-Open 9-87314 discloses, Japanese Patent Laid 7 -224079, JP Japanese Patent 2005-336092 discloses, etc., among some of the described supra literature, the general formula (7b), the general formula (9b) belonging to the zirconium compounds, and the like.
The metallocene compounds classified into crosslinked CpIndZr type shown in Table b-13 ~ Table b-20.

Figure JPOXMLDOC01-appb-T000057

Figure JPOXMLDOC01-appb-T000058

Figure JPOXMLDOC01-appb-T000059

Figure JPOXMLDOC01-appb-T000060

Figure JPOXMLDOC01-appb-T000061

Figure JPOXMLDOC01-appb-T000062

Figure JPOXMLDOC01-appb-T000063

Figure JPOXMLDOC01-appb-T000064

Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like. Further, when the use of these metallocene compounds as the component (A-2b), it is also possible to use two or more kinds.

In the inside of the specific compounds illustrated above as the metallocene compound as the component (A-2b), denoted by "A" to those preferred because polymerization activity is high. Further, as preferred in view of high polymerization activity, for example, dichloride 1-indenyl-2-indenyl - dimethylsilyl zirconium or Japanese Patent Laid-Open 2-76887 discloses, Japanese Patent Laid-Open 3-12406, JP- Japanese Patent Laid-Open 3-12407 discloses, Japanese Patent Laid-Open 3-12407 discloses, Japanese Patent Laid-Open 11-315089 and JP Japanese Patent 2009-143901 discloses, Japanese Kohyo 2005-507961 discloses, etc., of some of the described supra literature, by the general formula (2b) belonging to a silicon bridged bis (substituted cyclopentadienyl) zirconium compounds, the sum of the alkyl substituents of the two cyclopentadienyl rings 4 or more things, oxygen Motosumi described in Japanese Kohyo 2002-535339 Patent Publication belonging to the general formula (2b) Hydrogen group, sulfur-containing hydrocarbon group, among the hydrocarbon group-substituted silyl group such as a zirconium compound having a cyclopentadienyl ring substituted with, has a silicon bridged bis (substituted cyclopentadienyl) structure, and the two of those total substituents of the cyclopentadienyl rings of 4 or more including the oxygen-containing hydrocarbon group, Japanese Patent Laid-Open 8-59724 discloses, Japanese Patent Laid-Open 10-231314, JP- Japanese Patent 2003-105029 discloses, Japanese Patent 2004-352707 discloses, etc., among some of the described supra literature, the general formula (6b), the general formula (8b) belonging silicon bridged bis (substituted or unsubstituted indenyl) zirconium compounds, silicon bridged bis (substituted or unsubstituted azulenyl) zirconium compounds, silicon bridge (substituted or unsubstituted indenyl And (substituted or unsubstituted azulenyl) zirconium compounds, Japanese Kohyo 2002-535339 discloses, Japanese Patent 2004-352707 discloses, etc., among some of the described supra literature, the general formula (6b), general oxygen-containing hydrocarbon group belonging to the formula (8b), sulfur-containing hydrocarbon group, having a hydrocarbon group substituted with a substituted silyl group such as indenyl rings or azulenyl ring, silicon bridged bis (substituted or unsubstituted indenyl), silicon bridge bis (substituted or unsubstituted azulenyl), and zirconium compounds of silicon cross-linked (substituted or unsubstituted indenyl) (substituted or unsubstituted azulenyl), Japanese Patent Laid-Open 6-87922 discloses, Japanese Patent Laid-Open 8-92308, JP- Japanese Patent Laid-Open 9-87314 discloses, Japanese Patent Laid-Open 7-224079 and JP Japanese Patent 2005-33 6092 JP, etc., among some of the described supra literature, the general formula (7b), a zirconium compound belonging to the general formula (9b), the cyclopentadienyl ring and Fukuwa joined by a bridging group on the cyclopentadienyl ring with a total of the oxygen-containing hydrocarbon group, which may be substituents are two or more ones, and the like.

Similarly, in the specific compounds illustrated above as the metallocene compound as the component (A-2b), denoted by "B" preferred from the viewpoint of excellent formability. Further, as preferred from the viewpoint of excellent formability, for example, dichloride 1-indenyl-2-indenyl - dimethylsilyl zirconium or Japanese Patent Laid-Open 2-76887 discloses, Japanese Patent Laid-Open 3-12406, JP- Japanese Patent Laid-Open 3-12407 discloses, Japanese Patent Laid-Open 3-12407 discloses, Japanese Patent Laid-Open 11-315089 and JP Japanese Patent 2009-143901 discloses, Japanese Kohyo 2005-507961 discloses, etc., of some of the described supra literature, it belongs to the general formula (2b), and 2-position of at least one of the cyclopentadienyl rings is substituted with an alkyl group, and at least the other cyclopenta bridged bis any position of the dienyl ring is substituted with an alkyl group Jill having (alkyl substituted cyclopentadienyl) structure Onium compounds, are described in dimethylsilylenebis (2- (2-furyl) -3,5-dimethyl-cyclopentadienyl) zirconium dichloride above general formula (2b) belonging to Japanese Kohyo 2002-535339 JP such as oxygenated hydrocarbon group, sulfur-containing hydrocarbon group, among the zirconium compound having a cyclopentadienyl ring substituted with a hydrocarbon group-substituted silyl group such as the 2-position of at least one of the cyclopentadienyl rings is the free oxygen is substituted with a hydrocarbon group, or an alkyl group, and at least cross any position other cyclopentadienyl ring is substituted with the oxygen-containing hydrocarbon group, or an alkyl group of bis (substituted cycloalkyl zirconium compound having a pentadienyl) structure, Japanese Patent Laid-Open 8-59724 discloses, Japanese Patent 10- 31314 JP, Japanese Patent 2003-105029 discloses, Japanese Patent 2004-352707 discloses, etc., among some of the described supra literature, silicon belonging to the general formula (6b), the general formula (8b) crosslinked or carbon bridged bis (substituted or unsubstituted indenyl) zirconium compounds, silicon bridge or carbon bridged bis (substituted or unsubstituted azulenyl) zirconium compounds, silicon bridged or carbon bridge bridge (substituted or unsubstituted indenyl) (substituted or unsubstituted azulenyl ) zirconium compound and, Japanese Kohyo 2002-535339 discloses, Japanese Patent 2004-352707 discloses, etc., among some of the described supra literature, belong to the general formula (6b), the general formula (8b) oxygen-containing hydrocarbon group, a sulfur-containing hydrocarbon group, substituted with a hydrocarbon group-substituted silyl group such as By having indenyl ring or azulenyl ring, and or zirconium compound which their ring are bridged by the silicon bridging group or carbon bridging group, Japanese Patent Laid-Open 6-87922 discloses, Japanese Patent Laid-Open No. 8-92308 publication, Japanese Patent Laid-Open 9-87314 discloses, Japanese Patent Laid-Open 7-224079 and JP Japanese Patent 2005-336092 discloses, etc., among some of the described supra literature, the general formula (7b), a zirconium compound belonging to the general formula (9b), on the cyclopentadienyl ring having a cyclopentadienyl ring and Fukuwa joined by a bridging group, each be the oxygen-containing hydrocarbon group those having at least one or more substituents, or 2-position the oxygen-containing hydrocarbon group of the cyclopentadienyl ring, having at least sub ring also Such as those substituted with an alkyl group.

Further, in the specific compounds exemplified above, denoted by "C" in the more preferable in terms of excellent formability, as another example, for example, Japanese Patent Laid-Open 2-76887 discloses, Japanese Patent 3 -12406 and JP Japanese Hei 3-12407 discloses, Japanese Patent Laid-Open 3-12407 discloses, Japanese Patent Laid-Open 11-315089 and JP Japanese Patent 2009-143901 and JP Japan JP-T 2005 -507961 discloses, etc., among some of the described supra literature, belong to the general formula (2b), and which the 2-position of at least one of the cyclopentadienyl rings is substituted with an alkyl group, and at least Jill with 2 or 5-position of the bridged bis substituted with alkyl group (alkyl substituted cyclopentadienyl) structure of the other cyclopentadienyl ring Onium compounds, are described in dimethylsilylenebis (2- (2-furyl) -3,5-dimethyl-cyclopentadienyl) zirconium dichloride above general formula (2b) belonging to Japanese Kohyo 2002-535339 JP such as oxygenated hydrocarbon group, sulfur-containing hydrocarbon group, among the zirconium compound having a cyclopentadienyl ring substituted with a hydrocarbon group-substituted silyl group such as the 2-position of at least one of the cyclopentadienyl rings is the free oxygen is substituted with a hydrocarbon group, or an alkyl group, and at least the other 2-position or 5-position bridged bis substituted with the oxygen-containing hydrocarbon group, or an alkyl group of the cyclopentadienyl ring ( zirconium compound having a substituted cyclopentadienyl) structure, Japanese Patent Laid-Open 8-59724 discloses, Japanese Patent 1 -231314, JP Japanese Patent 2003-105029, JP Japanese Patent 2004-352707 discloses, etc., among some of the described supra literature, belong to the general formula (6b), the general formula (8b) silicon bridge or carbon bridged bis (substituted or unsubstituted indenyl) zirconium compounds, silicon bridge or carbon bridged bis (substituted or unsubstituted azulenyl) zirconium compounds, silicon bridged or carbon bridge bridge (substituted or unsubstituted indenyl) (substituted or unsubstituted azulenyl) zirconium compounds, and, and those 2-position of at least one of the indenyl ring or azulenyl ring is substituted by an alkyl group, Japanese Kohyo 2002-535339 discloses, Japanese Patent 2004-352707 JP , etc., among some of the described supra literature, the one General formula (6b), having the general formula (8b) belonging oxygen-containing hydrocarbon group, a sulfur-containing hydrocarbon group, has been the indenyl ring or azulenyl ring substituted at the 2-position of the position with a hydrocarbon group-substituted silyl group, and zirconium compounds their rings are bridged by the silicon bridging group or carbon bridging group and, Japanese Patent No. 6-87922 discloses, Japanese Patent Laid-Open 8-92308 discloses, Japanese Patent Laid-Open No. 9-87314 publication, Japanese Patent Laid-Open 7-224079 and JP Japanese Patent 2005-336092 discloses, etc., among some of the described supra literature, the general formula (7b), zirconium compounds belonging to general formula (9b) there are 2-position of the cyclopentadienyl ring with at least sub ring such as those which are substituted with the oxygen-containing hydrocarbon group, or an alkyl group.

Furthermore, in the specific compounds illustrated above, labeled "D" on the even more preferable in terms of excellent formability, as another example, for example, Japanese Patent Laid-Open 6-87922 discloses, Japanese Patent 8 -92308 and JP Japanese Hei 9-87314 discloses, Japanese Patent Laid-Open 7-224079 and JP Japanese Patent 2005-336092 discloses, etc., among some of the described supra literature, the general formula ( 7b), a zirconium compound belonging to the general formula (9b), such as those 2-position of the cyclopentadienyl rings is substituted with the oxygen-containing hydrocarbon group, or an alkyl group mentioned having at least sub ring It is.

Furthermore, in the specific compounds illustrated above, labeled "E" to those preferred in view of excellent moldability, as another example, for example, Japanese Patent Laid-Open 6-87922 discloses, Japanese Patent Laid-Open 8-92308 and JP Japanese Hei 9-87314 discloses, Japanese Patent Laid-Open 7-224079 and JP Japanese Patent 2005-336092 discloses, etc., among some of the described supra literature, the general formula (7b), a zirconium compound belonging to the general formula (9b), at least 2-position of the cyclopentadienyl ring with a sub rings such as those which are substituted with the oxygen-containing hydrocarbon group and the like.

Synthesis examples of the metallocene compound is a component according to the present invention (A-2b) are shown below, in these synthetic methods is not particularly limited.
For example, after the lithiated indene compound, is reacted with dichlorosilane compound, followed ligand by reaction with cyclopentadienyl lithium is obtained. The resulting ligand tetrakis (alkyl amide) zirconium, followed method is reacted with trimethylsilyl chloride and or a lithiated The resulting ligand, followed by and a method of reacting with zirconium tetrachloride.

IV-2. A second aspect of the olefin polymerization catalyst component of component (Ac) olefin polymerization catalyst component present invention comprising the present invention includes a component (Ac) to be subsequently defined as an essential component.
Component (Ac): crosslinking the cyclopentadienyl ring and the indenyl ring represented by the following general formula (1c), further metallocene compounds having a 4-position of a specified substituent of the indenyl ring

Figure JPOXMLDOC01-appb-C000065

Wherein (1c), M 1c indicates one of the transition metals Ti, Zr or Hf. X 1c and X 2c are each independently hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1c and Q 2c are each independently a carbon atom, a silicon atom or a germanium atom. R 1c are each independently, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four to form a ring together with Q 1c and Q 2c and at least two members out of R 1c it may be. m c is 0 or 1, if m c is 0, Q 1c is directly bonded to the conjugated 5-membered ring containing R 2c. R 2c and R 4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1 to 6 having 1 to 20 carbon atoms, 1 to 4 carbon atoms halogen-containing hydrocarbon group of 1-20, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom. R 3c represents a substituted aryl group represented by the following general formula (1-ac). ]

Figure JPOXMLDOC01-appb-C000066

Wherein (1-ac), Y 1c is the periodic table group 14 shows a group 15 or 16 atom.R 5c, R 6c, R 7c , R 8c and R 9c each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group of 1 to 20 carbon atoms containing an oxygen or nitrogen having 1 to 20 carbon atoms hydrocarbon group, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6, C 1 - 20 halogen-containing hydrocarbon group, or a hydrocarbon group-substituted silyl group having a carbon number of 1 ~ 20, R 5c, R 6c, R 7c, the R 8c and R 9c attached adjacent groups, their with bonded atoms may form a ring. n c is 0 or 1, if n c is 0, there is no substituent R 5c to Y 1c. p c is 0 or 1, if p c is 0, carbon atoms carbon atoms and R 9c which R 7c is attached is bound is directly attached. If Y 1c is a carbon atom, R 5c, R 6c, R 7c, R 8c, at least one of R 9c is not a hydrogen atom. ]

In the general formula (1c), M 1c of the metallocene compounds, Ti, represents Zr or Hf, M 1c of metallocene compound, preferably an Zr or Hf, M 1c of the metallocene compound, more preferably Zr represent.
Further, X 1c and X 2c are each independently hydrogen atom or a chlorine atom, a bromine atom, an iodine atom or a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxymethyl group, ethoxymethyl group, n- propoxymethyl group, i- propoxymethyl, n- butoxymethyl group, i- butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, an acetyl group, 1-oxopropyl group, 1-oxo -n- butyl group, 2- methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo - propyl group, a phenyl acetyl group, diphenylacetyl groups Benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, a 4-methoxyphenyl group, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-i- propyl aminomethyl group, bis (dimethylamino) methyl group, bis (di-i- propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methylimino group, ethylimino group, 1- (methylimino) ethyl group, 1- (phenylimino) ethyl , 1 - [(phenylmethyl) imino] ethyl group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, t-butoxy group, a phenoxy group, dimethylamino group, diethylamino group , di-n- propylamino group, di-i- propylamino group, di-n- butylamino group, Di i- butylamino group, di-t- butylamino group, and a diphenylamino group.
Specific examples of preferred X 1c and X 2c, a chlorine atom, a bromine atom, a methyl group, n- butyl group, i- butyl group, a methoxy group, an ethoxy group, i- propoxy, n- butoxy group, a phenoxy group, dimethylamino group, di-i- propylamino group. Among these specific examples, a chlorine atom, a methyl group, a dimethylamino group is particularly preferred.

Also, Q 1c and Q 2c are each independently a carbon atom, a silicon atom or a germanium atom. Preferably a carbon atom or a silicon atom. More preferably a silicon atom.
Furthermore, as the R 1c, independently, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , neopentyl group, cyclopentyl group, n- hexyl group, a cyclohexyl group, and a phenyl group. Further, as a case where R 1c form a ring together with Q 1c and Q 2c, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group cyclohexylene, sila cyclobutyl group, silacyclopentyl group, silacyclohexyl groups such as and the like.
Specific examples of preferred R 1c, when Q 1c and / or Q 2c is a carbon atom, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, include cyclobutylidene group, also, Q 1c and / or Q 2c If it is a silicon atom, a methyl group, an ethyl group, a phenyl group, and silacyclooctane butyl group.

Also, R 2c and R 4c represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, a 4-methylphenyl group, 3,5-dimethyl phenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2- chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclo Pentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6 - pentafluorophenyl group, 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethylsilyl group , triphenylsilyl group, diphenylmethyl silyl group, and a phenyl dimethylsilyl group.
Also, R 2c and R 4c is a hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, If it is a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, particularly polymerization activity becomes higher, preferably.
Preferred examples of R 2c and R 4c represents a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group , a cyclohexyl group, a phenyl group, 2-methyl-furyl group, include trimethylsilyl group. Among these specific examples, a hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, more preferably a trimethylsilyl group, a hydrogen atom, a methyl group, t- butyl group, a phenyl group, a trimethylsilyl group is particularly preferable.

R 3c substituents, a substituted aryl group having a structure represented by the general formula (1-ac), preferably, shows Ph group having a specific substituent or furyl groups, thienyl groups,. Specifically, 4-trimethylsilyl phenyl group, 4- (t-butyldimethylsilyl) phenyl group, 4- (3,5-bis-trimethylsilyl) phenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3,5 - dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 2-furyl group, 2- (5 - methyl) furyl group, 2- (5-t-butyl) furyl group, 2- (5-trimethylsilyl) furyl group, 2- (2,3-dimethyl) furyl, 2-benzofuryl group, 2-thienyl group, 2- (5-methyl) thienyl, 2- (5-t-butyl) thienyl, 2- (5-trimethylsilyl) thienyl, 2- (2,3-dimethyl) thienyl , And the like.

Further, in the general formula (1), m c is 0 or 1, if m c is 0, Q 1c is directly bonded to the conjugated 5-membered ring containing R 2c.

Metallocene compound of the present invention is preferably one represented by the following general formula (2c).

Figure JPOXMLDOC01-appb-C000067

In the above formula (2c) metallocene compounds represented by, M 1c, X 1c, X 2c, Q 1c, R 1c, R 2c and R 4c are, description of metallocene compounds represented by the above general formula (1c) it can be selected the same structure as the atoms and groups indicated by.Also, R 10c may be selected R 5c shown in the description of the metallocene compounds represented by the aforementioned general formula (1c), R 6c, R 7c, the same structure as the atoms and groups R 8c and R 9c .

Further, metallocene compounds of the present invention, like the well formula (2c) those represented by the following general formula (3c) preferred.

Figure JPOXMLDOC01-appb-C000068

In the above general formula (3c) metallocene compounds represented by, M 1c, X 1c, X 2c, Q 1c, R 1c, R 2c and R 4c are, description of metallocene compounds represented by the above general formula (1c) it can be selected the same structure as the atoms and groups indicated by.Also, R 12c, R 13c and R 14c are similar to the atoms and groups of R 5c, R 6c, R 7c , R 8c and R 9c shown in the description of the metallocene compounds represented by the above general formula (1c) it is possible to select the structure. And Z1c represents an oxygen atom or a sulfur atom.

Specific examples of the metallocene compounds represented by the general formula (3c) the general formula (4c) in Table c-1 ~ Table c-5, not limited thereto.

Figure JPOXMLDOC01-appb-C000069

Figure JPOXMLDOC01-appb-T000070

Figure JPOXMLDOC01-appb-T000071

Figure JPOXMLDOC01-appb-T000072

Figure JPOXMLDOC01-appb-T000073

Figure JPOXMLDOC01-appb-T000074

Zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like as preferred.

Further, in the inside of the specific compounds illustrated above, show preferred compounds are set forth below as the metallocene compound is an essential component (Ac). For example, Table c-1 in to Table c-5, 1c ~ 10c, 12c ~ 65c, 67c ~ 80c, 95c ~ 143c, include like.
Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like as preferred.

Further, in the inside of the specific compounds illustrated above as the metallocene compound is an essential component (Ac), show particularly preferred are set forth below. For example, Table c-1 in to Table c-5, 1c ~ 4c, 7c, 8c, 12c ~ 38c, 44c ~ 47c, 52c ~ 59c, 62c, 63c, 67c ~ 80c, 116c ~ 123c, 127c ~ 136c, 142c, 143c, and the like.
Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like as preferred.

Further, in the inside of the specific compounds illustrated above as the metallocene compound is an essential component (Ac), show preferred compounds are set forth below in particular point higher polymerization activity. For example, Table c-1 in to Table c-5, 1c ~ 8c, 12c ~ 38c, 44c ~ 47c, 52c ~ 63c, 67c ~ 80c, 116c ~ 123c, 127c ~ 136c, 142c, 143c, and the like are exemplified .
Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like as preferred.

Further, in the inside of the specific compounds illustrated above as the metallocene compound is an essential component (Ac), show preferred compounds are set forth below in terms of particularly excellent in moldability. For example, in Table c-1 ~ Table c-5, 1c ~ 4c, 7c ~ 10c, 12c ~ 59c, 62c ~ 65c, 67c ~ 80c, 95c ~ 143c, and the like.
Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like as preferred.

Further, when the use of these metallocene compounds as the component (Ac), it is also possible to use two or more kinds.

Synthesis of metallocene compounds:
Metallocene compound of the present invention, by a substituent or binding mode, can be synthesized by any method. An example of a typical synthetic route shown below.

Figure JPOXMLDOC01-appb-C000075

In the above synthetic route, Compound 1 with 4-trimethylsilyl-phenyl boronic acid, by performing the coupling reaction in the presence of a palladium catalyst, compound 2 is obtained. After anion of compound 2 in such one equivalent of n- butyl lithium, it is reacted with an excess of dimethyldichlorosilane, by distilling off the dimethyldichlorosilane unreacted compound 3 is obtained. The resulting compound 3 with sodium cyclopentadienylide is reacted with compound 4 is obtained. After Compound 4 was dianion of like two equivalents of n- butyl lithium, metallocene compounds 5 are obtained by reaction of a zirconium tetrachloride. Synthesis of the metallocene compounds obtained by introducing a substituent group, can be synthesized by using the corresponding substituted starting material instead of 4-trimethylsilyl-phenyl boronic acid, the corresponding boronic acid, such as 4-chlorophenyl boronic acid, 4- methoxyphenylboronic acid, 5-methyl-furyl-2-boronic acid, 4,5-dimethyl-furyl-2-boronic acid, using and 2-thienylboronic acid, respectively the 4-position of the indenyl ring corresponding substituents it can be introduced.

IV-3. Olefin polymerization catalyst component of the present invention (A-1b) and (A-2b) The present olefin polymerization catalyst of the invention or the olefin polymerization catalyst of the present invention comprising a catalyst component for olefin polymerization of the present invention (Ac), including olefin polymerization catalyst of the present invention comprises the following components (a) and (B), composed optionally, further comprise a component (C).
Component (A): an olefin polymerization catalyst component ingredients of the present invention as defined in the above (B): compound component which reacts with component (A) to produce a cationic metallocene compound (C): a particulate support will present invention the olefin polymerization catalyst will be described for each item (hereinafter, the olefin polymerization catalyst component of the present invention is sometimes referred to as component (a) or simply a.).

IV-3 (1). Component (B)
Olefin polymerization catalyst of the present invention, as component (B), the component reacts with the metallocene compound cationic metallocene compound to produce the (A) (hereinafter, sometimes, referred to as the component (B) or simply B. ) comprises, preferably comprises a component (B) and the particulate support (preferred component (C), hereinafter, may be simply referred to as C.).

One of the metallocene compound (A) reacts with to form a cationic metallocene compound (B), and organic aluminum oxy compound.
The organoaluminum oxy-compound, in the molecule, having Al-O-Al bonds, the number of bonds is usually 1 to 100, preferably in the 1-50 range. Such organoaluminum oxy-compounds are usually product obtained by reacting with water the organic aluminum compound.
The reaction of the organoaluminum with water is usually carried out in inert hydrocarbon (solvent). The inert hydrocarbon, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, aliphatic hydrocarbons such as xylene, although alicyclic hydrocarbons and aromatic hydrocarbons can be used, aliphatic hydrocarbons or it is preferred to use an aromatic hydrocarbon.

Organoaluminum compounds used for preparing the organoaluminum oxy-compound is a compound represented by the following general formula (11b) is either available, preferably trialkyl aluminum is used.
R 23b t AlX 21b 3-t ··· formula (11b)
(Wherein, R 23b is from 1 to 18 carbon atoms, preferably an alkyl group of 1 to 12, an alkenyl group, an aryl group, a hydrocarbon group such as an aralkyl group, X 21b represents a hydrogen atom or a halogen atom , t is an integer of 1 ≦ t ≦ 3.)

Alkyl group of trialkyl aluminum, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, but no problem either and dodecyl group, a methyl group it is particularly preferred is.
The organic aluminum compounds may be used in combinations of two or more.

The reaction ratio of water and organic aluminum compound (water / Al molar ratio) is 0.25 / 1 to 1.2 / 1, particularly preferably from 0.5 / 1 to 1/1, the reaction temperature generally -70 ~ 100 ° C., preferably in the range of -20 ~ 20 ° C.. The reaction time is usually 5 minutes to 24 hours, are chosen preferably in the range of 10 minutes to 5 hours. As the water required for the reaction, solely water not only may be utilized also crystal water or components of water are able to form in the reaction system contained copper sulfate hydrate, aluminum sulfate hydrate or the like.
Among the organic aluminum oxy compound as described above, those obtained by reacting an alkyl aluminum and water, usually referred to as aluminoxanes, (including those consisting essentially of methylaluminoxane (MAO)) particularly methylaluminoxane as the organoaluminum oxy compound, it is preferred.
Of course, as the organoaluminum oxy-compound, can also be used in combination of two or more of the organic aluminum oxy compound as described above, also, the organic aluminum oxy compound is a solution or dispersion in an inert hydrocarbon solvent mentioned above solution it may be used as well was.

As a component of an olefin polymerization catalyst component of the present invention (B), the use of the organoaluminum oxy-compound, or strain hardening degree of the resulting ethylene-based polymer (.lambda.max) increases, is a measure of the high molecular weight component content Mz / Mw (where, Z average molecular weight Mz is measured by GPC, Mw represents the same weight average molecular weight.) and is increased, since the moldability is more improved preferably.

Further, as another specific example of the metallocene compound (A) reacts with the cationic metallocene compound to form compound (B), include borane compounds and borate compounds.
Expressed more specifically the borane compounds, triphenyl borane, tri (o-tolyl) borane, tri (p- tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris ( p- fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl), tris ( perfluoroanthryl) borane, tris (Pafuruorobi Fuchiru) such as borane and the like.

Of these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro biphenyl) borane, tris (perfluoroanthryl) borane, tris (perfluoro-binaphthyl) are more preferable borane, more preferably tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( perfluoronaphthyl) borane, tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

Further, specific representative of a borate compound, the first example is a compound represented by the following general formula (12b).
[L 1b -H] + [BR 24b R 25b X 31b X 32b] - ··· formula (12b)
Wherein (12b), L 1b is a neutral Lewis base, H is a hydrogen atom, [L 1b -H] is ammonium, anilinium, a Bronsted acid such as phosphonium.
The ammonium, trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, trialkyl-substituted ammonium, such as tri (n- butyl) ammonium, di (n- propyl) ammonium, can be exemplified dialkylammonium such as dicyclohexylammonium.

As the anilinium, N, N- dimethylanilinium, N, N- diethyl anilinium, N, N-2,4,6 N such pentamethyl anilinium, N- dialkylanilinium can be exemplified.
Further, as the phosphonium, triphenyl phosphonium, tributyl phosphonium, tri (methylphenyl) phosphonium, triaryl phosphonium and tri (dimethylphenyl) phosphonium, and trialkyl phosphonium.

Further, in the formula (12b), R 24b and R 25b are each independently 6-20, preferably containing carbon atoms of 6 to 16, the same or different aromatic or substituted aromatic hydrocarbon group, may be linked to each other by a bridging group, as the substituent of the substituted aromatic hydrocarbon group, an alkyl group or a fluorine typified methyl group, an ethyl group, a propyl group, isopropyl group, chlorine, bromine, iodine the preferred halogen atoms.
Furthermore, X 31b and X 32 b are each independently hydride radicals, halide radicals, hydrocarbon group containing from 1 to 20 carbon atoms, the carbon of the the 1 to 20 substituted with one or more hydrogen atoms by a halogen atom a substituted hydrocarbon group containing an atom.

Specific examples of the compound represented by the general formula (12b), tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5 ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoro-naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6 ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6 Jifuruorofu Yl) borate, dimethylanilinium tetra (perfluoro-naphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5 - ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoro-naphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyl Tetra (perfluoro-naphthyl) borate, tripropyl ammonium tetra (pentafluorophenyl) borate, tripropyl ammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropyl ammonium tetra (perfluoro-naphthyl) borate, di (1 - propyl) ammonium tetra (pentafluorophenyl) borate, and the like can be exemplified dicyclohexylammonium tetraphenylborate.

Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro naphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (perfluoro-naphthyl) borate is preferred.

The second example of the borate compound is represented by the following general formula (13b).
[L 2b] + [BR 26b R 27b X 41b X 42b] - ··· formula (13b)
Wherein (13b), L 2b is carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert- butyl cation, pentyl cation, tropicity cation, benzyl cation, trityl cation, sodium cations, protons, and the like.Also, R 26b, R 27b, X 41b and X 42b are the same as defined in the general formula (12b).

Specific examples of the compounds, trityl tetraphenylborate, trityl tetra (o-tolyl) borate, trityl tetra (p- tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, trityl tetra (p- fluorophenyl) borate, trityl tetra (m-fluorophenyl) borate, trityl tetra (3,5-difluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, trityl tetra (2,6-di-fluoro methylphenyl) borate, trityl tetra (3,5-ditrifluoromethylphenyl) borate, trityl tetra (perfluoro-naphthyl) borate, tropicity tetraphenylborate, tropicity tetra (o-tolyl) Rate, Tropi tetra (p- tolyl) borate, tropicity tetra (m-tolyl) borate, tropicity tetra (o-fluorophenyl) borate, tropicity tetra (p- fluorophenyl) borate, tropicity tetra (m- fluorophenyl) borate, tropicity tetra (3,5-difluorophenyl) borate, tropicity tetra (pentafluorophenyl) borate, tropicity tetra (2,6-ditrifluoromethylphenyl) borate, tropicity tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) borate, NaBPh 4, NaB (o- CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) 4, Na B (o-F-Ph) 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) 4, NaB (2,6- (CF 3 ) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H + BPh 4 · 2 diethyl ethers, H + B (3,5-F 2 -Ph) 4 · 2 diethyl ether, H + B (C 6 F 5) 4 - · 2 diethyl ether, H + B (2,6- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (3,5- (CF 3) 2 -Ph) 4 · 2 diethyl ether, can be exemplified H + B (C 10 H 7 ) 4 · 2 diethyl ether it can.

Among these, trityl tetra (pentafluorophenyl) borate, trityl tetra (2,6-ditrifluoromethylphenyl) borate, trityl tetra (3,5-ditrifluoromethylphenyl) borate, trityl tetra (perfluoro-naphthyl) borate, Tropi tetra (pentafluorophenyl) borate, tropicity tetra (2,6-ditrifluoromethylphenyl) borate, tropicity tetra (3,5-ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) borate, NaB (C 6 F 5) 4 , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H + B (C 6 F 5 ) 4 - · 2 diethyl Ether, H + B (2,6- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (3,5- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B ( C 10 H 7) 4 · 2 diethyl ether.

More preferably, among these trityl tetra (pentafluorophenyl) borate, trityl tetra (2,6-ditrifluoromethylphenyl) borate, tropicity tetra (pentafluorophenyl) borate, tropicity tetra (2,6-di-fluoro methylphenyl) borate, NaB (C 6 F 5) 4, NaB (2,6- (CF 3) 2 -Ph) 4, H + B (C 6 F 5) 4 - · 2 diethyl ether, H + B ( 2,6- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (3,5- (CF 3) 2 -Ph) 4 · 2 diethyl ether, H + B (C 10 H 7) 4 · 2 diethyl ether.

As the catalyst component (B), the use of borane compounds and borate compounds, since the polymerization activity and copolymerizability is high, productivity is improved ethylene polymer having long chain branching.
Furthermore, as a component of an olefin polymerization catalyst (B), and the organoaluminum oxy-compound, also possible to use mixtures of the above borane compounds or borate compounds. Furthermore, the borane compound and the borate compound can also be used in combinations of two or more.
Further, as another specific example of the compound which reacts with the metallocene compound (A) to form a cationic metallocene compound (B), for example, clays that are described in Japanese Patent Laid-Open 8-127613 discloses such, clay minerals, ion-exchangeable layered compound, and inorganic silicates, solid oxide described in Japanese Kohyo 2002-515522 Patent Publication compounds, and the organoaluminum oxy-compound, the same operation as the borane compound and the borate compound compounds having a can be used as well with these.

IV-3 (2). Preferred components (C)
The preferred component (C) a particulate carrier which is an olefin polymerization catalyst of the present invention, inorganic carriers include particulate polymer carrier or a mixture thereof. Mineral support is a metal, metal oxide, metal chloride, metal carbonate, carbonaceous material or a mixture thereof, can be used.
Suitable metals which can be used in mineral support, for example, iron, aluminum, nickel, or the like.

Further, as the metal oxide, either alone oxide or composite oxide of the Periodic Tables 1 to 14 elements can be mentioned, for example, SiO 2, Al 2 O 3 , MgO, CaO, B 2 O 3, TiO 2, ZrO 2, Fe 2 O 3, Al 2 O 3 · MgO, Al 2 O 3 · CaO, Al 2 O 3 · SiO 2, Al 2 O 3 · MgO · CaO, Al 2 O 3 · MgO · SiO 2, Al 2 O 3 · CuO, Al 2 O 3 · Fe 2 O 3, Al 2 O 3 · NiO, can be exemplified a variety of natural or synthetic, such as SiO 2 · MgO alone oxide or composite oxide. Here, the above equation is not a molecular formula, a represents the only composition, structure and component ratio of the composite oxide used in the present invention is not limited in particular.
The metal oxide used in the present invention is not safe to have absorbed a small amount of water, also contain small amounts of impurities no problem.

As metal chloride, for example, an alkali metal chloride of an alkaline earth metals are preferred, particularly such as MgCl 2, CaCl 2 is especially preferred.
As the metal carbonate, alkali metal, alkaline earth metal carbonates are preferable, specifically, magnesium carbonate, calcium carbonate and barium carbonate.
The carbonaceous material, for example, carbon black, activated carbon and the like.
Or mineral support, each of which may be suitably used for the present invention, in particular metal oxides, silica, the use of such alumina preferred.

These mineral support, usually, 200 ~ 800 ° C., preferably from 400 to 600 air at ° C. or nitrogen, and fired in an inert gas such as argon, the amount of surface hydroxyl groups 0.8 ~ 1.5 mmol / g preferably used adjusted to the.
The properties of these inorganic carriers, is not particularly limited, usually, the mean particle size of 5 ~ 200 [mu] m, preferably 10 ~ 150 [mu] m, an average pore size of 20 ~ 1000 Å, preferably 50 ~ 500 Å, a specific surface area 0.99 ~ 1000 m 2 / g, preferably 200 ~ 700m 2 / g, pore volume 0.3 ~ 2.5cm 3 / g, preferably 0.5 ~ 2.0cm 3 / g, apparent specific gravity is 0.20 to 0 .50g / cm 3, preferably it is preferable to use an inorganic carrier having a 0.25 ~ 0.45g / cm 3.

Mineral support described above are, of course may be used as it is, trimethylaluminum these carriers pretreatment, triethyl aluminum, triisobutyl aluminum, tri-hexyl aluminum, tripropyl aluminum, tributyl aluminum, trioctyl aluminum, tridecyl aluminum, after contact with the organoaluminum oxy-compound containing an organoaluminum compound and Al-O-Al bonds, such as diisobutyl aluminum hydride, it can be employed.
Further, a powder of component (A) and component (B), it is also possible to use as the particulate support.

IV-3 (3). Metallocene compound is an essential component of an olefin polymerization catalyst component of the present invention preparation method invention olefin polymerization catalyst according to the (A), by reacting the metallocene compound (A), which is also an essential component generates a cationic metallocene compound is to compound (B), and, method of contacting the components in obtaining the olefin polymerization catalyst using the olefin polymerization catalyst component comprising a particulate carrier (C) is a preferred component is not particularly limited, for example, the following methods are arbitrarily employed.

(I) a metallocene compound (A), after contacting the metallocene compound (A) reacts with the cationic metallocene compound to produce a (B), contacting particulate carrier (C).
(II) a metallocene compound (A), after contacting the particulate carrier (C), contacting the metallocene compound (A) reacts with the cationic metallocene compound to produce a (B).
(III) metallocene compound (A) reacts with the cationic metallocene compound to produce (B), and after contacting the particulate carrier (C), contacting the metallocene compound (A).

A preferable process for in these contact methods and (I) (III), is the most preferred method of addition (I). In the above contact methods, the essential components are metallocene compound (A) (A-1b) as an essential component (A-2b) may be handled as a mixture, may be handled separately, for example, component (A- 1b) is a method of the above embodiment (I), component (a-2b) can be a method such as used in the method of the (III).
In any of the contact method, in an inert atmosphere is usually such as nitrogen or argon, generally benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene (usually carbon number 6 to 12), heptane, hexane, decane, dodecane , the presence of aliphatic or alicyclic hydrocarbon liquid inert hydrocarbon, such as (usually 5 to 12 carbon atoms), such as cyclohexane, a method of contacting the components under stirring or non-stirring is employed.
This contact, usually -100 ° C. - 200 ° C., preferably from -50 ° C. - 100 ° C., more preferably at 0 ° C. to 50 ° C. of temperature, 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably it is preferably performed in 30 minutes to 12 hours.

Further, the metallocene compound (A), upon contact of the metallocene compound (A) reacts with the cationic metallocene compound to produce (B) and particulate carrier (C), as described above, certain components are soluble or a sparingly soluble aromatic hydrocarbon solvent, any certain or components insoluble sparingly soluble aliphatic or alicyclic hydrocarbon solvents can be used.

In the case of the contact reaction between the components in stages, without removing the like solvent used in the previous paragraph, which may be directly used as a solvent of the subsequent catalytic reaction. Further, after the preceding stage of the catalytic reaction using a soluble solvent, certain components are insoluble or hardly soluble liquid inert hydrocarbon (e.g., aliphatic pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene hydrocarbons, with the addition of alicyclic hydrocarbon or aromatic hydrocarbon), the desired product after was collected as a solid, or temporarily some or all of the soluble solvent, was removed by means of drying desired after retrieving the product as a solid, a subsequent contact reaction of the desired product, can be carried out using any of the inert hydrocarbon solvents mentioned above. In the present invention, not prevent a plurality of times contact reaction of the components.

In the present invention, the metallocene compound (A), the metallocene compound (A) reacts with the cationic metallocene compound to produce (B), and the proportion of the particulate carrier (C) is not particularly limited, the following range is preferred.
The molar ratio of the metallocene compound as the component (A) (A-1b) and the component (A-2b), depending on the material properties required for the olefin polymer as a final product, but are set in any range usually when the total of both is 100, 1:99 to range of 99.9: 0.1, preferably from 5: 95-99.5: 0.5, more preferably from 10: 90 to 99.5: 0. 5, more preferably 20: 80-99.5: 0.5, particularly preferably 40: 60 to 99.2: 0.8. Component when (A-1b) is less than 1, because macromer generation amount missing long chain branching is not sufficiently formed, or not observed improvement in moldability to olefin polymer is a product, higher molecular weight order component to form a polymer (a-2b) is the main active species, conditions hydrogen is molecular weight modifier is large, that is, polymerization in adverse conditions to produce long chain branching is required, also molding or observed improvement in workability, because the polymer formed from the minor component (a-1b) product tends sticky become lower molecular weight is not preferable. See also, if component (A-1b) is greater than 99.9, the molecular weight of the polymer may become difficult to sufficiently large, long chain branching does not develop to a sufficient high molecular weight, improvement in moldability and it may not be, which is not preferable. However, the molar ratio of component (A-1b) and the component (A-2b), in the case where the same level of both the olefin polymerization activity is greatly different, because the selection is changed, the molar ratio is strictly objective it goes without saying that the material properties of the olefin polymer is to be optimized drives out to.

Metallocene compound (A) reacts with the cationic metallocene compound to produce compound as (B), in the case where using an organic aluminum oxy compound, the organoaluminum oxy-compound to the metallocene compound (A) in the transition metal (M) of aluminum atomic ratio (Al / M) is usually 1 to 100,000, preferably from 5 to 1000, more preferably preferably in the range of 50 to 200, in the case of using a borane compound and a borate compound, a transition in the metallocene compound to the metal (M), the atomic ratio of boron (B / M) is usually 0.01 to 100, preferably 0.1 to 50, more preferably is desirably selected in the range of 0.2 to 10.
Furthermore, as a compound to generate a cationic metallocene compound (B), an organoaluminum oxy compound, borane compounds, in the case of using a mixture of a borate compound, for each compound in the mixture of the transition metal (M) it is desirable to select in the same proportion and the Te.

The amount of the particulate carrier (C) is per transition metal 0.0001-5 mmol in the metallocene compound (A), preferably per 0.001 to 0.5 mmol, more preferably 0.01-0.1 mmol it is a per 1g.

Metallocene compound (A), the metallocene compound (A) reacts with the cationic metallocene compound to produce (B), and any of the above contacting method and particulate carrier (C) (I) ~ (III) mutually contacting, thereafter, to remove the solvent, it is possible to obtain an olefin polymerization catalyst as a solid catalyst. The removal of the solvent under normal pressure or reduced pressure, 0 - 200 ° C., preferably from 1 minute to 50 hours at 20 ~ 0.99 ° C., preferably is preferably performed in 10 minutes to 10 hours.

Incidentally, olefin polymerization catalysts can also be obtained by the following method.
(IV) metallocene compound (A) and contacting the particulate carrier (C) removing the solvent, and this as a solid catalyst component, an organoaluminum oxy-compound under polymerization conditions, borane compounds, borate compounds or mixtures thereof It is brought into contact.
(V) an organoaluminum oxy compound, borane compounds, are brought into contact with borate compounds or mixtures thereof and particulate carrier (C) to remove the solvent, which was a solid catalyst component, a metallocene compound under polymerization conditions (A) and It is brought into contact.
Above (IV), even if the method of contacting (V), component ratio, contacting conditions and solvent removal conditions are the same conditions it can be used.

Thus obtained olefin polymerization catalyst, no problem be used after the preliminary polymerization of the monomers as required.
Furthermore, olefin polymerization catalyst components or olefin polymerization catalysts of the present invention, further, the component (D): It is also preferred to include an organoaluminum compound. As such organic aluminum compounds, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, an organic aluminum compound, which is also described in the above general formula, such as ethyl aluminum dichloride (11b), diethylaluminum ethoxide, ethyl aluminum diethoxide, dimethyl aluminum ethoxide, a carbon number of 1 to 18, preferably from 1 to 12 alkoxide, an organic aluminum compound and the organoaluminum oxy-compound having an oxygen-containing hydrocarbon group such as alkenyloxy, containing branched alkyl modified organoaluminum compound or the like is used. Among these, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, preferably diethylaluminum ethoxide, triethylaluminum, triisobutylaluminum, more preferably diethylaluminum chloride, triethylaluminum, triisobutylaluminum still more preferably, triethylaluminum is particularly preferred.

IV-4. Catalyst for olefin polymerization according to the present invention uses the above-described olefin polymerization catalyst of the present invention, the copolymerization of homopolymerization or olefins and other olefins of the olefin, can be used.

Here, the olefin having 2 to 30 carbon atoms, is preferably included those 2 to 8, preferably ethylene or α- olefins include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like are exemplified, more preferably an ethylene homopolymer or a copolymer of ethylene and the α- olefin, more preferably, ethylene homopolymer, ethylene-propylene copolymerization, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, an ethylene-1-octene copolymer.
Olefins, it is also possible to copolymerize three or more kinds of olefins.
Copolymerization, alternating copolymerization, random copolymerization, no problem be any of block copolymer. When the copolymerization of ethylene and another α- olefin, the amount of the other α- olefin, which can be optionally selected in the range of 90 mol% or less of the total monomers, in general, 40 mol% hereinafter, chosen preferably from 30 mol% or less, more preferably in the range of 10 mol% or less. Of course, it is also possible to use small amounts of comonomers other than ethylene and α- olefin, in this case, styrene, 4-methylstyrene, styrenes such as 4-dimethylamino styrene, 1,4-butadiene, 1,5 having hexadiene, 1,4-hexadiene, dienes such as 1,7-octadiene, norbornene, cyclic compounds cyclopentene such as hexenol, hexenoic acid, oxygen-containing compounds such methyl octene acid, a polymerizable double bond of equal mention may be made of the compound.

In the present invention, the polymerization reaction, the catalyst, preferably in the presence of a supported catalyst, preferably at slurry polymerization, or gas phase polymerization can be carried out.
For slurry polymerization, substantially oxygen, in a state that refused water, isobutane, hexane, aliphatic hydrocarbons such as hexane and heptane, benzene, toluene, xylene and like aromatic hydrocarbons, cyclohexane, alicyclic and methyl cyclohexane in the presence or absence of an inert hydrocarbon solvent selected from the group hydrocarbons, it is polymerized ethylene and the like. Further, it goes without saying that the liquid monomer, such as liquid ethylene and liquid propylene may also be used as a solvent.
In addition, in the case of gas phase polymerization, introducing ethylene and the comonomer gas stream, flow, or the polymerization of ethylene or the like in the circulated reactor.
In the present invention, further preferred polymerization is a gas phase polymerization. The polymerization conditions, the temperature is 0 ~ 250 ° C., preferably 20 ~ 110 ° C., more preferably 60 ~ 100 ° C., the pressure is atmospheric pressure ~ 10 MPa, preferably normal pressure ~ 4 MPa, more preferably 0.5 ~ 2 MPa in the range of, as the polymerization time of 5 minutes to 10 hours, preferably normal to 5 minutes to 5 hours are employed.

The molecular weight of the produced polymer, the polymerization temperature, but it is possible to some extent regulated by varying the polymerization conditions the molar ratio or the like of the catalyst, the addition of hydrogen to the polymerization reaction system, to perform more effectively molecular weight regulator can.
Further, in the polymerization system, component intended for water removal can be carried out without any trouble be added a so-called scavenger.
As such scavengers include trimethyl aluminum, triethyl aluminum, organoaluminum compounds are also described in the above general formula (11b), such as triisobutyl aluminum, the organoaluminum oxy-compound, modified organic aluminum compound containing a branched alkyl, diethylzinc, organic zinc compounds such as dibutyl zinc, diethyl magnesium, dibutyl magnesium, organomagnesium compounds such as ethyl butyl magnesium, ethyl magnesium chloride, etc. Grignard compounds such as butyl chloride is used. Among these, triethyl aluminum, triisobutyl aluminum, ethylbutyl magnesium Preferably, triethylaluminum is particularly preferred.
The hydrogen concentration, monomer content, the polymerization pressure, also multistage polymerization method polymerization conditions at least two different stages of one another such as polymerization temperature, can be applied without any problem.

[V] A fourth aspect of the ethylene polymer of the manufacturing method of the present invention of the present invention, the metallocene-based polyolefin having a long chain branching of sufficient number and appropriate length, preferably a sufficient number and appropriate length of it is to provide a method for producing a metallocene polyethylene having long chain branching. Hereinafter, a fourth aspect of the present invention will be described for each item.

V-1. Process for producing an olefin polymer of an olefin polymerization catalyst present invention, the production method preferably ethylene polymer, olefin polymerization comprising comprises the following components (A) and (B), if desired, the component (C) It is carried out with the use a catalyst.
Component (A): at least any one of the following catalyst components (A-i) components described above IV-1 wherein (A-1b) and (A-2b) olefin polymerization catalyst component comprising (A- ii) the components described in IV-2 Section (Ac) olefin polymerization catalyst component comprising (a-iii) the following general formula (1d) olefin polymerization catalyst component comprising a metallocene compound represented by.

Figure JPOXMLDOC01-appb-C000076

Wherein (1d), M 1d represents any of the transition metals Ti, Zr or Hf. X 1d and X 2d are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1d and Q 2d are each independently a carbon atom, a silicon atom or a germanium atom. R 1d are each independently, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four to form a ring together with Q 1d and Q 2d and at least two members out of R 1d it may be. m d is 0 or 1, if m d is 0, Q 1d is directly bonded to the conjugated 5-membered ring containing R 2d and R 3d. R 2d and R 3d is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having silicon atoms 1-1 carbon atoms containing from 6 to 18 halogen containing 1 to 20 carbon atoms hydrocarbon group, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, not the least one hydrogen atom of R 2d. R 4d represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 5d is an atom or group bonded to the carbon atoms of R 4d, each independently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 1 containing silicon atoms 1-6 ~ 18 silicon-containing hydrocarbon group, a halogen-containing hydrocarbon group, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom having 1 to 20 carbon atoms. n d represents an integer of 0 to 10, if n d is 2 or more, at least two R 5d, together with binding to that carbon atom may form a ring. ]
Component (B): component compound component which reacts with the metallocene compound to form a cationic metallocene compound (A) (C): a particulate support

The olefin polymerization catalyst used in the production method of the ethylene polymer (A-iii) The present invention as described as shall contain the metallocene compound represented by the general formula (1d) and (Ad) as essential components it is characterized in.
In the general formula (1d), M 1d of the metallocene compounds, Ti, represents Zr or Hf, M 1d of metallocene compound, preferably an Zr or Hf, M 1d of the metallocene compound, more preferably Zr represent.
Further, X 1d and X 2d are each independently a hydrogen atom or a chlorine atom, a bromine atom, an iodine atom or a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, i - butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxymethyl group, ethoxymethyl group, n- propoxymethyl group, i- propoxymethyl, n- butoxymethyl group, i- butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, an acetyl group, 1-oxopropyl group, 1-oxo -n- butyl group, 2- methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo - propyl group, a phenyl acetyl group, diphenylacetyl groups Benzoyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, a 4-methoxyphenyl group, 2-furyl group, 2-tetrahydrofuryl group, dimethylaminomethyl group, diethylaminomethyl group, di-i- propyl aminomethyl group, bis (dimethylamino) methyl group, bis (di-i- propylamino) methyl group, (dimethylamino) (phenyl) methyl group, methylimino group, ethylimino group, 1- (methylimino) ethyl group, 1- (phenylimino) ethyl , 1 - [(phenylmethyl) imino] ethyl group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, t-butoxy group, a phenoxy group, dimethylamino group, diethylamino group , di-n- propylamino group, di-i- propylamino group, di-n- butylamino group, Di i- butylamino group, di-t- butylamino group, and a diphenylamino group.
Specific examples of preferred X 1d and X 2d, a chlorine atom, a bromine atom, a methyl group, n- butyl group, i- butyl group, a methoxy group, an ethoxy group, i- propoxy, n- butoxy group, a phenoxy group, dimethylamino group, di-i- propylamino group. Among these specific examples, a chlorine atom, a methyl group, a dimethylamino group is particularly preferred.

Also, Q 1d and Q 2d are each independently a carbon atom, a silicon atom or a germanium atom. Preferably a carbon atom or a silicon atom. More preferably silicon atom.
Furthermore, as the R 1d, each independently, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , neopentyl group, cyclopentyl group, n- hexyl group, a cyclohexyl group, and a phenyl group. Further, as a case where R 1d forms a ring together with Q 1d and Q 2d, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group cyclohexylene, sila cyclobutyl group, silacyclopentyl group, silacyclohexyl groups such as and the like.
Specific examples of preferred R 1d, when Q 1d or / and Q 2d is a carbon atom, a hydrogen atom, a methyl group, an ethyl group, a phenyl group, include cyclobutylidene group, also, Q 1d or / and Q 2d If it is a silicon atom, a methyl group, an ethyl group, a phenyl group, and silacyclooctane butyl group.

Furthermore, R 2d and R 3d is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, a 4-methylphenyl group, 3,5-dimethyl phenyl group, 4-t-butylphenyl group, 3,5-di -t- butyl phenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2- chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl group, 2,3-dibromo cyclo Pentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, 4-chlorophenyl group, 2,3,4,5,6 - pentafluorophenyl group, 4-trifluoromethylphenyl group, furyl group, tetrahydrofuryl group, 2-methyl-furyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethylsilyl group , triphenylsilyl group, diphenylmethyl silyl group, and a phenyl dimethylsilyl group.
Furthermore, R 2d and R 3d is a hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, If it is a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, particularly polymerization activity becomes higher, preferably. Additionally, R 2d can, if it is a hydrocarbon group having 1 to 20 carbon atoms, in terms of particularly excellent in formability of polyethylene, preferred.
Preferred examples of R 2d and R 3d is a hydrogen atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group , a cyclohexyl group, a phenyl group, 2-methyl-furyl group, and a trimethylsilyl group. Among these specific examples, a hydrogen atom, a methyl group, n- butyl group, t- butyl group, a phenyl group, more preferably a trimethylsilyl group, a hydrogen atom, a methyl group, t- butyl group, a phenyl group, a trimethylsilyl group is particularly preferable.

Specific examples of the condensed cyclopentadienyl structure formed from a cyclopentadienyl moiety and R 4d in which R 4d is bonded include the following partial structure (I) ~ (VI).
Among these specific examples, (I), (III), (VI) are preferred. Also, on these partial structures (I) ~ (VI), R 5d may be substituted.

Figure JPOXMLDOC01-appb-C000077

R 5d substituents, in addition to a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group, a neopentyl group, a cyclopentyl group, n- hexyl group, a cyclohexyl group, a phenyl group, a benzyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-t-butyl phenyl group, 3,5-dimethylphenyl group, 3,5-di -t- butyl phenyl group, a naphthyl group, anthracenyl group, bis (trimethylsilyl) methyl group, bis (t-butyldimethylsilyl) group, a bromomethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-cyclopentyl Group, 2,3-dibromo cyclopentyl group, 2-bromo-3-iodo-cyclopentyl group, 2,3-dibromo-cyclohexyl, 2-chloro-3-iodo cyclohexyl, 2-chlorophenyl group, a 4-chlorophenyl group, 2 , 3,4,5,6 pentafluorophenyl group, 2,6-dichloro-4-trimethylsilyl phenyl group, a trimethylsilyl group, tri t-butylsilyl group, di-t-butyl methyl silyl group, t- butyl dimethyl silyl group, triphenylsilyl group, diphenylmethyl silyl group, and a phenyl dimethylsilyl group.
Further, in R 5d are two or more, as an example of a case of forming a ring together with the bond to which carbon atoms, benzo [e] indenyl, benzo [f] indenyl, 6,7-dihydro inductor Seniru group, 5,5,7,7- tetramethyl-6,7-dihydro-indanyl cell group, 5,6,7,8-tetrahydro - benzo [f] indenyl, 5,6,7,8 tetrahydro-5,5,8,8-tetramethyl - such as benzo [f] indenyl group.
Specific examples of preferred R 5d, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- pentyl group, n- hexyl group, a cyclohexyl group, a phenyl group , naphthyl group, and a trimethylsilyl group.

Further, in the general formula (1d), m d is 0 or 1, if m d is 0, Q 1d is directly bonded to the conjugated 5-membered ring containing R 3d. Further, n d represents an integer of 0 to 10, if n d is 2 or more, at least two R 5d, together with binding to that carbon atom may form a ring.

As the olefin polymerization catalyst according to the present invention, essential metallocene compound of the component (Ad) is preferably one represented by the following general formula (2d).

Figure JPOXMLDOC01-appb-C000078

In the above general formula (2d) metallocene compounds represented by, M 1d, X 1d, X 2d, Q 1d, R 1d, R 2d, R 3d, R 4d and R 5d are, in the above general formula (1d) the same structure as the atoms and groups indicated in the description of the metallocene compounds represented, can be selected.

As the olefin polymerization catalyst according to the present invention, essential metallocene compound of the component (Ad) it is more preferably represented by the following general formula (3d).

Figure JPOXMLDOC01-appb-C000079

In the metallocene compound represented by the general formula (3d), M 1d, X 1d, X 2d, Q 1d, R 1d and R 2d are indicated in the description of the metallocene compounds represented by the above general formula (1d) the same structure as the atoms and groups can be selected.

In the production method of the ethylene polymer of the present invention, it exhibits the general formula Specific examples of the metallocene compounds of the essential components of the olefin polymerization catalyst (Ad) and (4d) in the following Table d-1 ~ Table d-4, they the present invention is not limited to. In Table d-1 ~ Table d-4, TMS is trimethylsilyl, Ind is an indenyl group, Cp represents a cyclopentadienyl group.

Figure JPOXMLDOC01-appb-C000080

Incidentally, the cyclopentadienyl ring of the metallocene compounds indicated in these examples, numbers indicating the position of the substituents on the indenyl ring are as follows (5d).

Figure JPOXMLDOC01-appb-C000081

Figure JPOXMLDOC01-appb-T000082

Figure JPOXMLDOC01-appb-T000083

Figure JPOXMLDOC01-appb-T000084

Figure JPOXMLDOC01-appb-T000085

Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, and the like.
Further, when the use of these metallocene compounds as an essential component (Ad), it is also possible to use two or more kinds.

In the inside of the specific compounds illustrated above, show preferred compounds are set forth below as the metallocene compound is an essential component (Ad). For example, in Table d-1 ~ Table d-4, 1d ~ 51d, 72d ~ 77d, 84d ~ 89d, 96d ~ 101d, 114d ~ 129d, 134d ~ 149d, and the like.
Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, as like are preferable, and the like.

Further, in the inside of the specific compounds illustrated above as the metallocene compound is an essential component (Ad), show particularly preferred are set forth below. For example, in Table d-1 ~ Table d-4, 1d ~ 6d, 17d, 18d, 46d ~ 49d, 115d, 117d, 118d, 121d, 123d, 125d, 127d, 129d, 135d, 137d, 139d, 141d, 143d, 145d, 147d, 149d, and the like.
Further, the zirconium of the above compounds, compounds obtained by replacing the titanium or hafnium, as like are preferable, and the like.

Further, in the inside of the specific compounds illustrated above as the metallocene compound is an essential component (Ad), show preferred compounds are set forth below in particular point higher polymerization activity. For example, in Table d-1 ~ Table d-4, 1d ~ 51,114d ~ 129d, 134d ~ 149d, and the like.

Further, in the inside of the specific compounds illustrated above as the metallocene compound is an essential component (Ad), show preferred compounds are set forth below in terms of particularly excellent in moldability. For example, in the table d-1 ~ Table d-4, 1d ~ 6d, 17d, 18d, 46d ~ 49d, 72d ~ 77d, 84d ~ 89d, 96d ~ 101d, 115d, 117d, 119d, 121d, 123d, 125d, 127d, 129d, 135d, 137d, 139d, 141d, 143d, 145d, 147d, 149d, and the like.

Synthesis examples of the metallocene compound is an essential component according to the present invention (Ad) are shown below, in these synthetic methods is not particularly limited.
For example, after the lithiated indene compound, it is reacted with dichlorosilane compound, followed ligand by reaction with the lithium salt of cyclopentadiene having a substituent is obtained. The resulting ligand tetrakis (alkyl amide) zirconium, followed method is reacted with trimethylsilyl chloride and or a lithiated The resulting ligand, followed by and a method of reacting with zirconium tetrachloride.

V-2. Olefin polymer, the physical properties of the ethylene-based polymer (features)
The polymerization process of the present invention, an olefin polymer or ethylene-based polymer is obtained as described below. Here, the description will be mainly when the ethylene polymer. In the present invention, the ethylene polymer refers to an ethylene homopolymer or an ethylene · alpha-olefin copolymer produced by the copolymerization described above.

Ethylene polymer produced by the production method of the ethylene polymer of the present invention, the [III] of the ethylene polymer column in defined conditions of sections satisfies at least condition (B-4 ') to. That is, the ethylene-based polymer .lambda.max (2.0) 1.2 to 30.0 preferably 1.5 to 20.0 more preferably 2.0-10.0, more preferably 2.4 it is to 6.0, and particularly preferably from 3.0 to 5.0. Incidentally, description of .lambda.max (2.0) satisfactory the ethylene polymer is already omitted here because it is as described in the section of the above conditions (A-4) and conditions (B-4) to.

Ethylene polymer produced in the present invention, with respect to conventional ethylene polymers, melt property has been improved, a significant feature to have excellent formability.
In general, polyethylene, film molding, blow molding, but is processed into industrial products by biasing type method via a molten state, such foam molding, this time, extensional flow properties a great influence on the ease of formability it is well known to give.
That is, a narrow molecular weight distribution, polyethylene having no long chain branching, because of the low melt strength is poor moldability, whereas a polyethylene having an ultra-high molecular weight component and long chain branching component, strain hardening (strain during melt extension hardening), i.e., extensional viscosity at high strain side has a sharp rising characteristics, polyethylene showing this characteristic significantly is said to be excellent in moldability.

Index The elongation viscosity characteristics as a method for quantitatively expressing, there is a method of calculating the ratio of the extensional viscosity of the elongational viscosity and after strain hardening before strain hardening strain hardening degree as (.lambda.max), representing the non-linearity of elongational viscosity as useful. When the λmax value is large, for example, there is an effect that can increase or prevent uneven thickness or breaking by blowing in the products in film molding or blow molding, or enables high-speed molding, the closed cell content during foam molding, molding goods strength improvements, design improvement, weight reduction, improvement of the molding cycle, the benefits of such thermal insulation improvement can be obtained.

Ethylene polymer produced in the present invention has a very distinctive elongational viscosity characteristics and molecular weight distribution and intrinsic viscosity characteristic based on the characteristic long chain branched structure, further, the ethylene polymer of the present invention ethylene polymer produced by the production method, 'in addition to, the above conditions (B-1 condition (B-4)'), (B-2 "), (B-3), (B-5 ), (B-7), of the (B-8) and (B-9), preferably at least any one or more, more preferably two or more, more preferably three or more, particularly preferably five above, and most preferably satisfies all of the ethylene polymer produced in the present invention, with respect to conventional ethylene polymers, melt property is particularly improved, has excellent moldability, rigidity, impact strength , so that the excellent mechanical properties such as transparency.

In the following examples and comparative examples illustrate the invention in more detail, but to demonstrate the superiority of excellence and construction of the present invention of the present invention, the invention is limited to these examples not.
The measurement methods used in Examples and Comparative Examples are as follows. Further, the following catalyst synthesis step and the polymerization step, all performed under purified nitrogen atmosphere, and the solvent used was used was dehydrated and purified over molecular sieve 4A.

[Strain hardening degree measuring method of the ethylene-based polymer]
Strain hardening degree of elongational viscosity (.lambda.max), using the rheometer was measured by the method of the described herein. Prior to the creation of the test piece was carried out dissolution and reprecipitation of the polymer by the following procedure.
Introducing xylene 300ml two-necked flask was attached a condenser 500 ml, was carried out with nitrogen bubbling for 30 minutes at room temperature. Polymer 6.0 g of 2,6-di -t- butyl-hydroxy toluene (BTH) was introduced 1.0 grams. Under a nitrogen atmosphere, and stirred at 125 ° C. 30 minutes, the polymer was completely dissolved in xylene. The xylene solution of the polymer is dissolved is poured in ethanol 2.5L, to precipitate a polymer. The polymer was collected by filtration and dried at 80 ° C. in a vacuum dryer.

[Measurement of terminal double bond number]
Determination of terminal double bonds, to prepare a pressed film, an infrared absorption spectrum (IR) using a device manufactured by Shimadzu Corporation FTIR-8300, 910 cm -1 is the absorption of out-of-plane deformation vibrations of monosubstituted alkenes It is calculated from the following equation from the absorbance of the peak.
The number of terminal double bonds (number / 1000 per carbon) = 1.14 × ΔA / d / t
Here, .DELTA.A the absorbance peak of 910 cm -1, d is the film density (g / cm 3), t is the film thickness (mm).

[Measurement of extractable content]
It was dissolved sample orthodichlorobenzene (0.5mg / mLBHT pieces) at 140 ° C. and a solution. It was cooled 100 ° C. at 8 ° C. / min cooling rate after introduction into TREF column 140 ° C., and cooled to continue -15 ° C. at 4 ° C. / min cooling rate and held 60 minutes. Thereafter, ortho-dichlorobenzene is the solvent (0.5mg / mLBHT pieces) through the column at a flow rate of 1 mL / min, the components dissolved in orthodichlorobenzene -15 ° C. in a TREF column eluted 10 minutes, then the column with heating rate of 100 ° C. / time heated linearly to 140 ° C., to obtain an elution curve.

apparatus;
(TREF section)
TREF column: 4.3mmφ × 150mm stainless steel column Column filler: 100 [mu] m surface deactivated glass beads heating system: aluminum heat block Cooling system: Peltier element (cooling of the Peltier element is water-cooling)
Temperature distribution: ± 0.5 ℃
Temperature controller: manufactured) CHINO digital program adjusting meter KP1000
(Valve oven)
Heating system: Air bath type oven at measurement temperature: 140 ° C.
Temperature distribution: ± 1 ℃
Valve: six-way valve, 4-way valve (Sample injection section)
Injection method: loop injection method Injection volume: loop size 0.1ml
Inlet heating system: aluminum heat block at measurement temperature: 140 ° C.
(Detection unit)
Detector: wavelength fixed type infrared detector FOXBORO Co. MIRAN 1A
Detection wavelength: 3.42μm
Hot flow cell: LC-IR for Micro Flow Cell, optical path length 1.5 mm, window shape 2 [phi × 4 mm length round, synthetic sapphire window plate at measurement temperature: 140 ° C.
(Pump section)
The feed pump: Senshu Scientific Co., Ltd. SSC-3461 pump measurement conditions;
Solvent: ortho-dichlorobenzene (0.5mg / mLBHT containing)
Sample concentration: 5mg / mL
Sample injection volume: 0.1mL
Solvent flow rate: 1 mL / min

[Evaluation Method of Film]
(1) in compliance with the tensile modulus JIS K7127-1999, the tensile modulus when the 1% deformation in the processing direction (MD direction) and the width direction (TD direction) of the film of the film was measured.
(2) The film impact filmy test piece was fixed to a holder having a diameter of 50 mm, is struck by the penetrating portion of the defined tip diameter (hemispherical 25.4Mmfai), were measured energy (J / mm) required for Penetration . It indicates that this value is better larger as impact strength.
Tester was used which is equipped with a 90 ° arcuate arm which can be attached to the penetrating portion according to JIS P8134, and the tip.
(3) Transparency (haze)
In compliance with JIS K7105-1981, it was measured. The smaller the value, the better the transparency.
(4) Tear strength (Elmendorf tear method)
In conformity with JIS K7128-1991, the tear strength of the processing direction (MD direction) and the width direction of the film (TD direction) of the film (N / mm) was measured.

Molding conditions blown film and moldability Evaluation Method]
In forming a 30μm film using the blown film production apparatus having the following 30mmφ extruder (molding apparatus), the molding under the following conditions, by forming a blown film, it was evaluated.
Device: inflation molding apparatus extruder screw diameter: 30 mm?
Die diameter: 25mmφ
Extrusion amount: 10kg / hr
Die lip gap: 2.0mm
Take-up speed: 6.0m / min blow-up ratio: 2.0
Molding resin temperature: 170-190 ° C. (described in Example)
Film thickness: 30μm
Cooling ring: single slit air ring

In forming a 50μm film using the blown film production apparatus having the following 50mmφ extruder (molding apparatus), the molding under the following conditions, by forming a blown film, it was evaluated.
Device: inflation molding apparatus extruder screw diameter: 50 mm [phi]
Die diameter: 75mmφ
Extrusion amount: 20kg / hr
Die lip gap: 3.0mm
Take-up speed: 15m / min blow-up ratio: 2.0
Molding resin temperature: 170-190 ° C.
Film thickness: 50μm
Cooling ring: two-stage air-cooling ring

EXAMPLE 1a (a)]
(1) ethylene polymer (A-1) prepared in the Preparation of metallocene catalyst A-1]
The catalyst preparation device provided with an electromagnetic induction stirrer, toluene 1000ml purified under nitrogen, tetraethoxy zirconium (Zr (OEt) 4) the 22g and indene 75g and methyl butyl cyclopentadiene 88g addition, tripropylamine while maintaining the 90 ° C. aluminum 100g was dropped over a period of 100 minutes, then allowed to react for 2 hours at the same temperature. After cooling to 40 ° C., and stirred for 2 hours was added 3200ml methylalumoxane solution in toluene (concentration 2.5 mmol / ml). Then advance 450 ° C. for 5 hours calcined silica (Grace Co., # 952, surface area 300m 2 / g) of 2000g was added. After stirring 1 hour at room temperature and a nitrogen blow and vacuum dried at 40 ° C., flow give sex of a good solid catalyst a-1.

Production of Ethylene-1-hexene copolymer]
Molar ratio of 1-hexene / ethylene 0.018, hydrogen / ethylene molar ratio 2.9 × 10 -4, a nitrogen concentration of 30 mol%, was prepared the total pressure 0.8 MPa, a temperature of 80 ° C. , gas phase continuous polymerization apparatus (inner volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersing agent) 1.5 kg) triethylaluminum in hexane to (0.03 mmol / ml) was fed at 7 ml / h, while maintaining the gas composition and temperature constant, polymerization was carried out by intermittently supplying the solid catalyst a-1 as production per hour is about 320 g. Activity was 420 g / (g catalyst · MPa · h), was measured for physical properties of the resulting ethylene-based polymer (A-1), MFR2.0g / 10 min, density 0.918 g / cm 3 met It was.

(2) an ethylene-based polymer (B-1) prepared in the Preparation of metallocene catalyst B-1]
Dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride cyclopentadienyl - with (3-methylindenyl) dimethyl silane, synthesized according to the procedure described in Macromolecules 1995,28,3771-3778 did.
Under a nitrogen atmosphere, charged silica 5 grams of calcined 5 hours at 600 ° C. in 200ml two-necked flask, and drying under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 0.99 ° C.. Under a nitrogen atmosphere 100ml two-necked flask which is separately prepared, placed synthesized dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride 51.8 milligrams above, were dissolved in dehydrated toluene 13.4ml and stirred for an additional 30 minutes added 20% methylaluminoxane / toluene solution 8.6ml of Albemarle Corporation at room temperature. While the entered was 200ml two necked flask vacuum-dried silica was heated and stirred in an oil bath at 40 ° C., it was added the total amount of toluene solution of the complex and methylaluminoxane reactant. After stirring for 1 hour at 40 ° C., to obtain a solid catalyst B-1 distilled off under reduced pressure and toluene solvent while heating to 40 ° C..

Production of Ethylene-1-hexene copolymer]
The ethylene-1-hexene gas phase continuous copolymerization using the above solid catalyst B-1 was conducted. That is, the temperature 75 ° C., hexene / ethylene molar ratio 0.012, hydrogen / ethylene molar ratio 1.5 × 10-3, 24 mol% of the nitrogen concentration, total pressure vapor phase continuous polymerization device was prepared in 0.8MPa (the internal volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersion agent) 1.8 kg) to be a solid catalyst in constant intermittently supplied while gas composition and temperature at a rate of 0.38 g / time polymerization went. Moreover, it was fed hexane diluted solution 0.03 mol / L of triethyl aluminum (TEA) to maintain the cleanliness of the system to the gas circulation line with 7 ml / hr. As a result, the average production rate of the polyethylene thus formed was a 420 g / hour. MFR and density of each 0.8 g / 10 min of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg (B-1), was 0.914 g / cm 3.

(3) producing a mixture ratio of the polyethylene resin composition 1a is an ethylene-based polymer (A-1) is 95 wt%, the polyethylene resin ethylene polymer (B-1) consists of a 5 wt%, a mixer mixed homogenized at the.
Then, the resulting mixture was melt-kneaded in a twin-screw extruder, the extrudate solidified and granulated. For finally obtained granular polyethylene resin composition 1a, the evaluation of the film formability and film properties were conducted by the method of forming a film of 50μ described above. The results are shown in Table 1a-1 and Table 1a-2.

Example 1a (b)]
The mixing ratio of the ethylene-based polymer, ethylene polymer (A-1) is 90% by weight, ethylene polymer, except that (B-1) was set to be 10% by weight, Example 1a (a) (1) in the same manner to (3) were carried out manufacturing and film forming of the polyethylene resin composition 1b. The results are shown in Table 1a-1 and Table 1a-2.

Example 1a (c)]
The mixing ratio of the ethylene-based polymer, ethylene polymer (A-1) is 80% by weight, ethylene polymer, except that (B-1) was set to be 20% by weight, Example 1a (a) (1) in the same manner to (3) were carried out manufacturing and film forming of the polyethylene resin composition 1c. The results are shown in Table 1a-1 and Table 1a-2.

Comparative Example C1a (a)]
In Example 1a (c), in place of the ethylene-based polymer (B-1), the high-pressure radical process low-density polyethylene (manufactured by Japan Polyethylene Corporation LF240; MFR = 0.7g / 10 min, density 0.924 g / cm 3 ) were carried out manufacturing and film forming of the polyethylene resin composition C1a in the same manner as in example 1a but using (c). The results are shown in Table 1a-1 and Table 1a-2.

Comparative Example C1a (b)]
In Example 1a (c), instead, a commercially available ethylene polymer having long chain branching (manufactured by Sumitomo Chemical Co. CB2001 of the ethylene-based polymer (B-1); MFR = 1.8g / 10 min, density 0 .918g / cm 3) were carried out manufacturing and film forming of the polyethylene resin composition C1b in the same manner as in example 1a but using (c). The results are shown in Table 1a-1 and Table 1a-2.

Comparative Example C1a (c)]
In Example 1a (a), without using the ethylene polymer (B-1), polyethylene was prepared in analogy to ethylene polymer (A-1) alone in Example 1a (a) (3) manufacturing and film forming resin composition C1c were performed. The results are shown in Table 1a-1 and Table 1a-2.

Example 2a]
In Example 1a (c), instead, a commercially available ethylene-based polymer produced by magnesium titanium composite Ziegler catalyst (A-2) of the ethylene polymer produced in a metallocene catalyst (A-1) (A -2) (manufactured by Japan polyethylene Corporation UF230; MFR = 1.0g / 10 minutes, except for using a density 0.921 g / cm 3 of ethylene-1-butene copolymer) in the same manner as in example 1a (c) It was carried out manufacturing and film forming of the polyethylene resin composition 2 Te. The results are shown in Table 1a-1 and Table 1a-2.

Comparative Example 2a]
In Example 2a, without the use of ethylene polymer (B-1), it was carried out manufacturing and film forming of the polyethylene resin composition C2 at ethylene polymer (A-2) alone. The results are shown in Table 1a-1 and Table 1a-2.

EXAMPLE 3a (a)]
(1) ethylene polymer (B-3) prepared in the Preparation of metallocene catalyst B-3]
As the metallocene complexes, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) in place of zirconium dichloride 51.8 mg, dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride 46.6 mg When rac- dimethylsilylene bis (indenyl) zirconium dichloride (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a solid catalyst B-3 in the same manner except for using 5.6 mg (2) of example 1a (a) It was.

Production of Ethylene-1-hexene copolymer]
The solid catalyst B-3 using Example 1a (a) the same ethylene-1-hexene gas phase continuous copolymerization and (2) were performed. That is, the temperature 75 ° C., hexene / ethylene molar ratio 0.007, hydrogen / ethylene molar ratio 2.5 × 10 -3, the nitrogen concentration 20 mol%, the total pressure gas phase continuous polymerization device was prepared in 0.8MPa (the internal volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersion agent) 1.8 kg) in the solid catalyst with a constant intermittently supplied while gas composition and temperature at a rate of 0.18 g / time polymerization went. Moreover, it was fed hexane diluted solution 0.03 mol / L of triethyl aluminum (TEA) to maintain the cleanliness of the system to the gas circulation line with 7 ml / hr. As a result, the average production rate of the polyethylene thus formed was a 300 g / hour. MFR and density of each 0.3 g / 10 min of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg (B-3), was 0.921 g / cm 3.

(2) the ethylene polymer produced in Production Example 1a of the polyethylene resin composition 3a of (a) (1) (A-1) 90 wt% and above (1) in the ethylene polymer obtained ( the B-3) a polyethylene resin comprising 10 wt%, was mixed homogenized in a mixer.
Then, the resulting mixture was melt-kneaded in a twin-screw extruder, the extrudate solidified and granulated. For finally obtained granular polyethylene resin composition 3a, the evaluation of the film formability and film properties were conducted by the method of forming a film of 30μ described above. The results are shown in Table 2a-1 and Table 2a-2.

Example 4a (a)]
(1) ethylene polymer (B-4) prepared in the Preparation of metallocene catalyst B-4]
As metallocene complexes, in place of dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride 51.8 mg, rac- ethylenebis indenyl zirconium dichloride (Strem Chemicals, Ltd. Inc.) 52.5 mg use, after Similarly methylaluminoxane was hexane and 30 minutes of reaction with toluene solvent and (2) of example 1a (a), N which is separately prepared, N- dimethylanilinium tetrakis (pentafluorophenyl) borate 201 milligrams of 10ml except carrying were allowed to dehydrated toluene solution added to an additional 30 minutes reaction the silica in the same manner as (2) of example 1a (a) to obtain a solid catalyst B-4.

Production of Ethylene-1-hexene copolymer]
It was produced ethylene-1-hexene copolymer using the above solid catalyst B-4. That is, the induction stirring device with 2L autoclave isobutane 800 mL, 1-hexene 22 mL, added triethylaluminum 0.20 mmol, the temperature was raised to 75 ° C., and H 2 was added 130 mL, of ethylene partial pressure was further introduced ethylene 1 It was kept at .4MPa. Then, 54mg of the solid catalyst B-4 to pressurized nitrogen, ethylene partial pressure 1.4 MPa, was continued for 120 min polymerization keeping the temperature 75 ° C., the polymerization by the addition of ethanol to stop. Incidentally, during the polymerization reaction was conducted additional feed of H2 and 1-hexene at a delivery rate proportional to the ethylene consumption rate. As a result, polymerization started after 10 minutes and the polymerization at the end of the autoclave gas phase portion of the H 2 / C 2 (hydrogen / ethylene) molar ratio is 0.21%, respectively, of 0.35% was additionally supplied 1-hexene the amount was 28mL. Thus obtained ethylene polymer (B-4) is 205g, the MFR and density of each 0.3 g / 10 min, it was 0.923 g / cm 3.

(2) similar to the preparation of ethylene-based polymer of the polyethylene-based resin composition 4a of the ethylene-based polymer in place of (B-3) (B-4) except for using the Example 3a in (a) (2) to produce a polyethylene resin composition 4a in the in were evaluated film moldability and film physical properties. The results are shown in Table 2a-1 and Table 2a-2.

Example 5a (a)]
(1) ethylene polymer (B-5) prepared in the Preparation of metallocene catalyst B-5]
Under a nitrogen atmosphere, charged silica 10 g was calcined for 5 hours at 600 ° C. in 200ml two-necked flask, and drying under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 0.99 ° C.. Separately under a nitrogen atmosphere 100ml two-neck flask prepared, placed in Tris indenyl zirconium hydride 46mg and (0.1 mmol) of tris benzoindenyl zirconium hydride 118mg of (0.2 mmol), was dissolved in dehydrated toluene 20 ml, further stirred for 30 minutes was added 20% methylaluminoxane / toluene solution 14.0ml of Albemarle Corporation at room temperature. With heating and stirring entered the 200ml two necked flask vacuum-dried silica in an oil bath at 40 ° C., it was added the total amount of toluene solution of the two complexes and methylaluminoxane reactant above. After stirring for 1 hour at 40 ° C., and the toluene solvent while heating to 40 ° C. to obtain a solid catalyst B-5 distilled off under reduced pressure.

Production of Ethylene-1-hexene copolymer]
The solid catalyst B-5 using Example 1a (a) the same ethylene-1-hexene gas phase continuous copolymerization and (2) were performed. That is, the temperature 80 ° C., hexene / ethylene molar ratio 0.020, hydrogen / ethylene molar ratio 4.7 × 10 -4, 26mol% nitrogen concentration, total pressure vapor phase continuous polymerization device was prepared in 0.8MPa (the internal volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersion agent) 1.8 kg) to be a solid catalyst in constant intermittently supplied while gas composition and temperature at a rate of 0.19 g / time polymerization went. Moreover, it was fed hexane diluted solution 0.03 mol / L of triethyl aluminum (TEA) to maintain the cleanliness of the system to the gas circulation line with 7 ml / hr. As a result, the average production rate of the polyethylene thus formed was a 260 g / hour. MFR and density of each 0.3 g / 10 min of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg (B-5), was 0.922 g / cm 3.

(2) similar to the preparation of ethylene-based polymer of the polyethylene-based resin composition 5a the ethylene polymer in place of (B-3) except that (B-5) was used in Example 3a in (a) (2) to produce a polyethylene resin composition 5a in the which was evaluated film moldability and film physical properties. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C3a (a)]
Instead of the ethylene-based polymer (B-3), the production of high-pressure radical process low-density polyethylene polyethylene resin composition in the same manner as in, except for using the (manufactured by Japan Polyethylene Corporation LF240) Example 3a (2) C3a and the evaluation of the film formability and film properties were conducted. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C4a (a)]
In (1) of Example 4a (a), N, N- dimethylanilinium except that was not used tetrakis pentafluorophenyl borate in the same manner as in Example 4a (a) ethylene polymer (B-C4) It was evaluated production and film moldability and film physical properties of the polyethylene resin composition C4a. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C5a]
In Example 3a (a), without using the ethylene polymer (B-3), polyethylene was prepared in analogy to ethylene polymer (A-1) alone in Example 3a in (a) (2) the evaluation of the production and film moldability and film physical properties of the resin composition C5 was carried out. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C6a]
In Example 5a (a), without using the ethylene polymer (A-1), polyethylene was prepared in analogy to ethylene polymer (B-5) alone in Example 3a (a) (2) the evaluation of the production and film moldability and film physical properties of the resin composition C6 was carried out. The results are shown in Table 2a-1 and Table 2a-2.

Example 3a (b)]
In (2) of Example 3a (a), 80 wt% of mixing ratio of the ethylene-based polymer (A-1) and the ethylene polymer (B-3): except for using 20 wt% Example 3a ( It was evaluated production and film moldability and film physical properties of the polyethylene resin composition 3b in the same manner as in (2) of a). The results are shown in Table 2a-1 and Table 2a-2.

Example 4a (b)]
Example 4a of (a) in (2), 80 wt% of the mixing ratio of the ethylene-based polymer (A-1) and the ethylene polymer (B-4): except for using 20 wt% Example 4a ( It was evaluated production and film moldability and film physical properties of the polyethylene resin composition 4b in the same manner as in (2) of a). The results are shown in Table 2a-1 and Table 2a-2.

Example 5a (b)]
Example 5a: (a) in (2), 80 wt% of the mixing ratio of the ethylene-based polymer (A-1) and the ethylene polymer (B-5): except for using 20 wt% Example 5a ( It was evaluated production and film moldability and film physical properties of the polyethylene resin composition 5b in the same manner as in (2) of a). The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C3a (b)]
In Comparative Example C3a (a), ethylene polymer (A-1) and 80 wt% of the mixing ratio of the high-pressure radical process low-density polyethylene: Production of polyethylene resin composition C3b similarly except for using 20 wt% and films were evaluated moldability and film physical properties. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C7a]
Instead of the ethylene-based polymer (A-1), the molar ratio of hexene / ethylene 0.017, hydrogen / except that ethylene ratio molar ratio was set to 2.1 × 10 -4 Example 1a of (a) (1) and except for using the ethylene polymer was prepared in the same manner (a-3), to evaluate the production and film moldability and film physical properties of the polyethylene resin composition C7 in the same manner as Comparative example C5a It was. The results are shown in Table 2a-1 and Table 2a-2.

Example 5a (c)]
70 wt% of the mixing ratio of the ethylene-based polymer (2) of Example 5a (a) (A-1) and the ethylene polymer (B-5): except for using 30 wt% Example 5a (a ) of (2) and in the same manner were evaluated production and film moldability and film physical properties of the polyethylene resin composition 5c. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C8a]
(1) ethylene polymer (A-4) of the manufacturing hexene / ethylene molar ratio of 0.011, except that the molar ratio of hydrogen / ethylene ratio and 3.4 × 10 -4 Example 1a (a) It was produced ethylene polymer (a-4) in the same manner as in (1).

(2) ethylene polymer (B-C8) preparation of the preparation of the metallocene catalyst B-C8]
Dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride instead dimethylsilylenebis Lido [4-phenyl-2- (2-furyl) - indenyl] is carried out except for using zirconium dichloride 95.6 mg in analogy to the preparation of metallocene catalyst B-1 of example 1a in (a) (2), was prepared solid catalyst B-C8. Incidentally, dimethylsilylene bis [4-phenyl-2- (2-furyl) - indenyl] zirconium dichloride was synthesized according to the procedure described in JP Japanese Kohyo No. 2002-535339.

Production of Ethylene-1-hexene copolymer]
It was produced ethylene-1-hexene copolymer using the above solid catalyst B-C8. That is, the induction stirring device with 2L autoclave isobutane 800 mL, 1-hexene 30 mL, triethylaluminum 2mmol addition, the temperature was raised to 75 ° C., of H2 was added 95 mL, further ethylene partial pressure by introducing ethylene 1.4MPa keeping was. Then, 27mg of the solid catalyst B-4 with pressurized nitrogen, ethylene partial pressure 1.4 MPa, was continued for 90 minutes polymerization keeping the temperature 75 ° C., the polymerization by the addition of ethanol to stop. Incidentally, during the polymerization reaction was conducted additional feed of H2 and 1-hexene at a delivery rate proportional to the ethylene consumption rate. As a result, H2 / C2 (hydrogen / ethylene) respectively, a molar ratio of 0.15% of the autoclave gas phase portion of the polymerization terminated and the polymerization initiator 10 minutes after, 0.14% additional supply was 1-hexene amount was 19mL. Thus obtained ethylene polymer (B-C8) is 113 g, the MFR and density each 0.05 g / 10 min, it was 0.894 g / cm 3.

(3) above, instead of producing ethylene polymer of the polyethylene resin composition C8 using the ethylene polymer in place of (A-1) to (A-4), ethylene polymer (B-5) except for using an ethylene-based polymer (B-C8) manufactures polyethylene resin composition C8 was prepared in analogy to example 5a (c), were evaluated film moldability and film physical properties. The results are shown in Table 2a-1 and Table 2a-2.

Comparative Example C9a]
(1) performing an ethylene-based polymer (A-4) In a similar manner the ethylene-1-hexene gas phase continuous copolymerization and (2) of Example 1a (a) using the preparation of the solid catalyst B-5 of the It was. That is, the temperature 85 ° C., hexene / ethylene molar ratio 0.016, hydrogen / ethylene molar ratio 6.2 × 10 -4, 30mol% nitrogen concentration, total pressure vapor phase continuous polymerization device was prepared in 0.8MPa (the internal volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersion agent) 1.8 kg) to be a solid catalyst in constant intermittently supplied while gas composition and temperature at a rate of 0.36 g / time polymerization went. Moreover, it was fed hexane diluted solution 0.03 mol / L of triethyl aluminum (TEA) to maintain the cleanliness of the system to the gas circulation line with 7 ml / hr. As a result, the average production rate of the polyethylene thus formed was a 400 g / hour. MFR and density of each 5.9 g / 10 min of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg (B-5), was 0.927 g / cm 3.

(2) using the ethylene polymer instead of producing ethylene polymer of the polyethylene resin composition C9 (A-1) to (A-5), compared instead of the ethylene-based polymer (B-5) examples of ethylene-based polymer produced in (2) of C8a except for using (B-C8) the manufactures polyethylene resin composition C9 in the same manner as in example 5a (c), the film moldability and film physical properties evaluation was carried out. The results are shown in Table 2a-1 and Table 2a-2.

EXAMPLE 6a (a)]
(1) ethylene polymer (A-6) of the manufacturing hexene / 0.011 molar ratio of ethylene, hydrogen / mole ratio of ethylene ratio except for using 2.7 × 10 -4 Example 1a ( It was produced ethylene polymer (a-6) in the same manner as in (1) of a).

(2) do the ethylene-based polymer (B-6) In a similar manner the ethylene-1-hexene gas phase continuous copolymerization Production above Example 5a (a) (1) of. However, the temperature 65 ° C., hexene / ethylene molar ratio 0.025, hydrogen / ethylene molar ratio 9.3 × 10 -4, the nitrogen concentration 24 mol%, and a total pressure of 0.8 MPa. As a result, the average production rate of the polyethylene thus formed was a 290 g / hour. MFR and density of each 0.3 g / 10 min of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg (B-6), was 0.906 g / cm 3.

(3) Alternatively, each of the ethylene-based polymer (A-6) and ethylene polymer produced ethylene polymer of the polyethylene resin composition 6 (A-1) and the ethylene polymer (B-5) except for using (B-6) in the same manner as in example 5a (c) carried out the production of polyethylene resin composition 6 was evaluated for film forming property and film properties. The results are shown in Table 3a-1 and Table 3a-2.

Comparative Example C10a (a)]
Ethylene polymer instead of (A-1), 1- hexene / molar ratio 0.013 for ethylene, hydrogen / except that ethylene ratio molar ratio was set to 2.3 × 10 -4 Example 1a (a ) of (1) and a similar manner ethylene polymers produced (except that a-7) was used, the evaluation of the production and film moldability and film physical properties of the polyethylene resin composition C10 in the same manner as Comparative example C5a It was carried out. The results are shown in Table 3a-1 and Table 3a-2.

EXAMPLE 7a (a)]
(1) ethylene polymer (A-7) of the manufacturing magnesium titanium composite Ziegler catalyst (A-2) an ethylene polymer produced by continuous gas phase polymerization with (A-7) (MFR = 1 .5g / 10 min, an ethylene-1-butene copolymer having a density of 0.936 g / cm 3) was used.

(2) Alternatively, each of the ethylene-based polymer (A-7) and ethylene polymer produced ethylene polymer of the polyethylene resin composition 7 (A-1) and the ethylene polymer (B-3) (B-6) except for using the prepared polyethylene resin composition 7 in the same manner as in example 3a (a), were evaluated film moldability and film physical properties. The results are shown in Table 3a-1 and Table 3a-2.

Comparative Example C11a (a)]
The in Example 7a (a), in place of the ethylene-based polymer (B-6), using the same high-pressure radical process low-density polyethylene in Comparative Example C1a (a), the ethylene-based polymer (A-7) production and film moldability and film physical properties of the high-pressure radical process low-density mixing ratio of polyethylene 80 wt% and except for using 20 wt% example 7a in (a) (2) and the polyethylene resin composition in the same manner C11 evaluation of was carried out. The results are shown in Table 3a-1 and Table 3a-2.

Comparative Example C12a (a)]
(1) it was subjected to ethylene polymer (B-C9) Similarly ethylene-1-hexene gas phase continuous copolymerization Production above Example 1a (a) (1) of. However, the temperature 65 ° C., hexene / ethylene molar ratio 0.025, a hydrogen / ethylene molar ratio was 2.6 × 10 -4. As a result, the average production rate of the polyethylene thus formed was a 320 g / hour. MFR and density of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg each 1.0 g / 10 min, was 0.906 g / cm 3.

(2) In Comparative Production Example of the polyethylene resin composition C12 C11a (a), the ethylene polymer instead of the ethylene-based polymer (B-7) (B-C9) and the high-pressure radical process low-density polyethylene (Nippon polyethylene Corporation; MFR = 0.8g / 10 min, a mixture of a density 0.924 g / cm 3) (mixing ratio 66 wt%: 34 wt%) was used, the mixture with the ethylene polymer (a-7) except that the mixing ratio was 62 wt% and 38 wt% of the out the production of the polyethylene resin composition C12 in the same manner as in (2) of example 7a (a).
That is, the ethylene polymer (A-7), the ethylene polymer (B-C9), the three components of the high-pressure radical process low-density polyethylene, after mixing homogenization in a mixer, the resulting mixture two was melt-kneaded at screw extruder, the extrudate solidifies, granulated, the finally obtained granular polyethylene resin composition C12, film moldability and film physical properties method of forming a film of 30μ was the evaluation was carried out. The results are shown in Table 3a-1 and Table 3a-2.

Comparative Example C13a (a)]
In Comparative Example C11a (a), using the Example 2a ethylene polymer instead of the ethylene-based polymer (A-7) to (A-2), ethylene polymer (A-2) and the high-pressure except that the mixing ratio of the radical process low-density polyethylene and 90 wt% and 10 wt% in the same manner as (2) of example 7a (a) to produce a polyethylene resin composition C13, film moldability and film physical properties evaluation of was carried out. The results are shown in Table 3a-1 and Table 3a-2.

Example 8a]
(1) ethylene polymer (B-8) prepared in the Preparation of metallocene catalyst B-8]
As the metallocene complexes, dimethylsilylene (cyclopentadienyl) instead of (3-methylindenyl) zirconium dichloride 51.8 mg, dimethylsilylene (cyclopentadienyl) [4- (4-trimethylsilyl-phenyl) indenyl] zirconium dichloride except for using 68.7 milligrams to obtain a solid catalyst B-8 in the same manner as in (2) of example 1a (a).

Production of Ethylene-1-hexene copolymer]
The solid catalyst B-8 Example 1a using in (a) the same ethylene-1-hexene gas phase continuous copolymerization and (2) were performed. That is, the temperature 75 ° C., hexene / ethylene molar ratio 0.004, hydrogen / ethylene molar ratio 5.5 × 10 -3, 20mol% nitrogen concentration, total pressure vapor phase continuous polymerization device was prepared in 0.8MPa (the internal volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersion agent) 1.8 kg) to be a solid catalyst in constant intermittently supplied while gas composition and temperature at a rate of 0.57 g / time polymerization went. Moreover, it was fed hexane diluted solution 0.03 mol / L of triethyl aluminum (TEA) to maintain the cleanliness of the system to the gas circulation line with 12 ml / hr. As a result, the average production rate of the polyethylene thus formed was a 288 g / hour. MFR and density of each 0.2 g / 10 min of the ethylene polymer obtained after generating a polyethylene or cumulative 5kg (B-8), was 0.920 g / cm 3.

(2) polyethylene resin composition 8a commercial ethylene polymer produced by the production of magnesium-titanium composite Ziegler catalyst (A-2) of (A-2) (manufactured by Japan Polyethylene Corporation UF230; MFR = 1.0g / 10 min, density 0.921 g / cm 3 of ethylene-1-butene copolymer) 80 wt% and the ethylene polymer obtained in the above (1) (B-8) a polyethylene resin consisting of 20 wt% It was mixed homogenized in a mixer.
Then, the resulting mixture was melt-kneaded in a twin-screw extruder, the extrudate solidified and granulated. For the polyethylene resin composition 8a of the finally obtained granular, the evaluation of the film formability and film properties were conducted by the method of forming a film of 50μ described above. The results are shown in Table 4a-1 and Table 4a-2.

Example 9a]
In the same manner as in Example 8a (2), it was subjected to production and film forming evaluation polyethylene resin composition. However, the same commercial ethylene polymer (A-2) using a 90 wt% and the ethylene polymer (B-8) 10 wt%.

Comparative Example C14a]
Example 9a, instead of the ethylene-based polymer (B-8), high-pressure radical process low-density polyethylene; use (manufactured by Japan Polyethylene Corporation LF240 MFR = 0.7g / 10 min, density 0.924 g / cm 3) except that the implemented a manufacturing and film forming of the polyethylene resin composition C14a analogously to example 8a. The results are shown in Table 4a-1 and Table 4a-2.

Comparative Example C15a]
Example 9a, ethylene polymer instead of (B-8), a commercially available ethylene polymer having long chain branching (manufactured by Sumitomo Chemical Co., Ltd. CU5001; MFR = 0.3g / 10 min, density of 0.922 g / cm 3) a was used instead was carried manufacturing and film forming of the polyethylene resin composition C15a analogously to example 8a. The results are shown in Table 4a-1 and Table 4a-2.

Figure JPOXMLDOC01-appb-T000086

Figure JPOXMLDOC01-appb-T000087

Figure JPOXMLDOC01-appb-T000088

Figure JPOXMLDOC01-appb-T000089

Figure JPOXMLDOC01-appb-T000090

Figure JPOXMLDOC01-appb-T000091

Figure JPOXMLDOC01-appb-T000092

Figure JPOXMLDOC01-appb-T000093

(Consideration by the results in Table 1a-1 and Table 1a-2)
An example of using the embodiment 1a (a) ~ Comparative Example C1a (c), a typical metallocene catalyzed ethylene-1-hexene copolymer produced in a film applications.
That is, the comparative example is illustrative that currently blended about 20% high-pressure radical polymerization method polyethylene as a technique to be performed normally well commercial level to improve the film's physical properties of the copolymer C1a (a), the ethylene polymer in the invention (B) similarly 20% blended with example 1a (c), a reduction in resin pressure has been seen, it was excellent in melt flowability. Further, as the film properties, tensile modulus and haze comparable, Nachi Suwa, while a degree hips and transparency same film, that impact strength is weak high 40%, excellent film impact strength obtained it is clear that is. The ethylene-based polymer (B) Similarly about 20% blend of an ethylene-based copolymer are not in a manufactured long chain branch-containing ethylene copolymer present invention by a transition metal catalyst that are currently commercially available was exemplified in a comparative example C1a (b), although the effect of the resin pressure drop obtained in the same manner, the impact strength is very small, the impact strength is much poorer the film with polyethylene-based resin composition according to the invention and which, it was not good enough even transparency obtained in the present invention.
Although blends of the ethylene-based polymer (B) in the present invention is conducted with a small illustrate embodiments 1a than the above example (a) and Example 1a (b), the ethylene-based polymer (B) Blend Comparative example C1a (c) without degrading the various performances of the elastic modulus and impact strength of the obtained resin pressure and film that did not improve the remarkably transparency and a haze value of from about 18% to 8% weak it was clear that the effect can be obtained.

Moreover, the comparison of Comparative Example 2a Example 2a, in the case of using a general Ziegler catalyzed ethylene-butene copolymer prepared by a film applications, an example of a case of applying the technique of the present invention Indicated.
That is, the ethylene-1-butene copolymer prepared by Ziegler catalysts, Examples 2a to ethylene polymer (B) was blended 20% in the present invention as in the example of the above-described metallocene catalyst, ethylene heavy while improving the impact strength of the obtained resin pressure and film in Comparative example 2a that did not blend coalesce (B), and the effect of the haze value is improved remarkably transparency and from about 15% to 6% give was an excellent effect to be.

(Consideration by the results of Table 2a-1 and Table 2a-2)
In Example 3a (a) ~ Comparative Example C7a, similar to the experimental examples shown in Table 1a-1 and Table 1a-2, to a common metallocene catalyst produced ethylene-1-hexene copolymer as a film applications in using, but it is planned experimental examples for suitable performance by applying design techniques is to clarify that the resulting polyethylene resin composition of the present invention, the ethylene polymer of the present invention to be used as (B), an illustration of applying those produced by different metallocene catalysts.
That is, Example 3a (a), Example 4a (a), in Example 5a (a), ethylene polymer ethylene polymer of the present invention produced by each different metallocene catalysts to (B) in the present invention the performance of the film due to the polyethylene resin composition obtained by blending 10% (a), the addition of example 3a (b), example 4a (b), in example 5a (b), the 20% the same film performance obtained by blending illustrates as compared with the case of the same amount blended high-pressure polyethylene each. In an embodiment of the polyethylene resin composition of the present invention, the resin pressure has seen decline or same level, was excellent in melt flowability. Further, as the film properties, tensile modulus comparable, Nachi Suwa, in condition that the waist comparable film, although transparency is is recessed from by blending some high-pressure polyethylene, a sufficiently practical has been improved to a level that can withstand, and impact strength are improved to nearly 10% to 80% strength, it was clear that good film impact strength. Further, not the ethylene polymer (B) in a known long chain branch-containing ethylene copolymer produced by the silica-supported methylalumoxane catalyst is widely known bridged bis indenyl zirconocene complex present invention Comparative example is illustrative blended similarly ethylene copolymer C4a (a), although is obtained improving minor impact strength, haze is deteriorated 10%, difficulty in practical use in view of film clarity there is a risk that lead to.

In Example 5a (c) ~ Comparative Example C9a, the ethylene polymer (A) in the present invention and an example of a combination of ethylene polymer (B) in the present invention is embodiment 5a (c), comparison as an example, the comparative example C8a is an example of a combination of ethylene polymer not according to the invention in that no ethylene polymer (a) and the long chain branching in the present invention, the in having a long chain branching in that no ethylene-based polymer with long chain branches are not ethylene polymer (a) of the invention is an example in which a combination of ethylene polymer not ethylene polymer (B) of the present invention Comparative example C9a and an experimental example was designed for the purpose of each comparison. Compared to a present invention embodiment 5a (c), in the comparative example, or resin pressure has become large to the contrary, by or observed improvement in film clarity at all, it can be seen undesirable.

(Consideration by the results in Table 3a-1 and Table 3a-2)
In Example 6a (a) ~ Comparative Example C13a (a), similarly to the experimental example shown in Table 1a-1 and Table 1a-2, Ya typical metallocene catalyzed ethylene prepared in 1-hexene copolymer general Ziegler catalyzed ethylene-butene copolymer prepared in when used as a film applications, that suitable performance by applying the design techniques of the polyethylene resin composition of the present invention can be obtained specifically is a designed experiment examples to. Ethylene polymer density of (B) to be lower than in the embodiment described above, which is a density A / density B was designed polyethylene resin composition so as to increase, as a result, extremely impact strength a planned exemplified in order to prove that excellent moldings can be obtained.
That is, typical metallocene catalyst example was directed to improvements in manufacturing ethylene-1-hexene copolymer with 6a (a) are ethylene-having almost the same MFR, density and film impact strength 1- to Comparative example is an example of a hexene copolymer alone C10a (a), the resin pressure of about 25% even be reduced, it indicates that further improvement in transparency can be realized, the present invention advantages of the polyethylene resin composition is apparent.
Furthermore, typical examples 7a of Ziegler catalyzed ethylene-butene copolymer prepared by the targeted (a), when the ethylene polymer of low density in the present invention (B) was blended, high pressure compared to Comparative example is an example of a polyethylene resin composition C11a (a) having a comparable MFR and density obtained by blending law polyethylene, is slightly improved in the tensile modulus of the resin pressure and film observed, although receding than with transparency blends of slightly high-pressure polyethylene, are improved to a level to withstand practical use sufficiently, and impact strength are also improved more than 40%, excellent in impact strength the film is clear that to obtain improvement effects of high impact strength, Comparative example C12 is an illustration of a ternary blend compositions developed aiming the same purpose It was those exceeding the impact strength of (a).
From the above, rationality and significance of the configuration requirements of the present invention, and it is clear superiority over the prior art of the present invention.

Synthesis of metallocene compound [Synthesis Example 1] dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride as described in Example 1 of Synthesis Japanese Patent Laid-Open 09-87314 discloses the (metallocene compound 11) It was synthesized according to the procedure.
Referring to the procedure described for the synthesis Macromolecules 1995,28,3771-3778 of Synthesis Example 2] dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride (metallocene compound 12), in the ligand synthesis It was synthesized using 1-methyl indene, instead of indene.
Was synthesized according to the procedure described in the synthesis Macromolecules 1995,28,3771-3778 of Synthesis Example 3] dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride (metallocene compound 13).
Referring to the procedure described for the synthesis Macromolecules 1995,28,3771-3778 of Synthesis Example 4] dimethylsilylene (cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride (metallocene compound 14), ligand It was synthesized using 1-t-butyl-indene instead of indene in the synthesis.
Referring to the procedure described for the synthesis Macromolecules 1995,28,3771-3778 of Synthesis Example 5] dimethylsilylene (cyclopentadienyl) (benzo [e] indenyl) zirconium dichloride (metallocene compound 15), in the ligand synthesis It was synthesized using benzo [e] indene instead of indene.

Referring to the procedure described for the synthesis Macromolecules 1995,28,3771-3778 of Synthesis Example 6] dimethylsilylene (cyclopentadienyl) (3-t-butylcyclopentadienyl) zirconium dichloride (metallocene compound 16), distribution It was synthesized using t- butyl cyclopentadiene instead of indene in ligand synthesis.
Synthetic commercial products of Synthesis Example 7 dimethylsilylene bis (cyclopentadienyl) zirconium dichloride (metallocene compound 17) was purchased from Wako Pure Chemical Industries, Ltd..
In Synthesis Example 8] dimethylsilylene (cyclopentadienyl) (2- (5-methyl-2-furyl) indenyl) zirconium dichloride Example 4 Synthesis Japanese Patent 2012-025664 discloses a (metallocene compound 21) It was synthesized according to the procedure described.
Synthesis Japanese Patent of Synthesis Example 9] dimethylsilylene (cyclopentadienyl) (2- (5-methyl-2-furyl)-4-(4-t-butylphenyl) indenyl) zirconium dichloride (metallocene compound 22) It was synthesized according to the procedure described in example 3 of open 2012-025664 JP.
[Synthesis Example 10] Racemic - dimethylsilylenebis (2- (5-trimethylsilyl-2-furyl) -4,5-dimethyl-cyclopentadienyl) Synthesis of Japan JP-T-2002-535339 zirconium dichloride (metallocene compound 23) It was synthesized according to the procedure described in example 10 of JP.

[Synthesis Example 11] Racemic - Synthesis Japanese Patent Application of dimethylsilylenebis (2- (5-methyl-2-furyl)-4-(4-i-propylphenyl) indenyl) zirconium dichloride (metallocene compound 24) 2011- synthesizing a ligand according to the procedure described in synthesis example 1 of Patent 008,562 were synthesized using zirconium tetrachloride instead of hafnium tetrachloride.
[Synthesis Example 12] Racemic - dimethylsilylenebis exemplary synthesis Japanese Patent 2002-47313 JP-(2- (5-methyl-2-furyl) -4- (phenyl) indenyl) zirconium dichloride (metallocene compound 25) examples was synthesized according to the procedure described in 1.
In Synthesis Example 13] isopropylidene (4-t-butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride Example 1 Synthesis Japanese Patent Laid-Open 05-148284 discloses the (metallocene compound 26) It was synthesized according to the procedure described.
[Synthesis Example 14] Racemic - a synthesis commercially available dimethyl (indenyl) zirconium dichloride (metallocene compound 27) was purchased from Wako Pure Chemical Industries, Ltd..
It was synthesized according to the procedure described in dimethylsilylene synthesis Organometallics 1994,13,954-963 Len bis (2-methyl-4-phenyl indenyl) zirconium dichloride (metallocene compound 28) - Synthesis Example 15] racemic.
Was synthesized according to the procedure described in isopropylidene bis (indenyl) zirconium dichloride Example 1 and Example 3 Synthesis Japanese Patent Laid-Open 09-20694 discloses the (metallocene compound 29) - Synthesis Example 16] racemic.
And the synthesis of commercially available products of ethylene bis (indenyl) zirconium dichloride (metallocene compound 30) was purchased from Wako Pure Chemical Industries, Ltd. - [Synthesis Example 17] racemic.

[Example 1b]
(1) Under Preparation nitrogen atmosphere the solid catalyst, put silica 5 grams of calcined 5 hours at 600 ° C. in 200ml two-necked flask, and drying under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 0.99 ° C.. The metallocene compound 11 22.7 mg metallocene compound 21 placed and 23.9 milligrams under a nitrogen atmosphere 100ml two-necked flask which is separately prepared, and dissolved in dehydrated toluene 13.4 ml. It was stirred Albemarle Corp. 20% methylaluminoxane / Toluene solution 8.6ml was added 30 minutes to a toluene solution of the metallocene compound at room temperature. With heat and stirring entered the 200ml two necked flask vacuum-dried silica in an oil bath at 40 ° C., it was added the total amount of toluene solution of the metallocene compound and methylaluminoxane reactant. After stirring for 1 hour at 40 ° C., to obtain a solid catalyst distilled off under reduced pressure and toluene solvent while heating to 40 ° C..

(2) to produce ethylene-1-hexene copolymer with the solid catalyst obtained in the preparation of the solid catalyst prepared above ethylene-1-hexene copolymer (1).
That is, the induction stirring device with 2L autoclave isobutane 800 mL, 1-hexene 50 mL, triethylaluminum 0.20mmol addition, the temperature was raised to 75 ° C., maintaining the ethylene partial pressure to 1.4MPa by introducing ethylene.
Then, the solid catalyst 57mg obtained in the above (1) with pressurized nitrogen, ethylene partial pressure 1.4 MPa, was continued for 60 minutes polymerization keeping the temperature 75 ° C., ethanol polymerization was quenched by the addition.
Incidentally, during the polymerization reaction was carried out additional supply of proportional at a feed rate of 1-hexene to ethylene consumption rate.
As a result, H 2 / C 2 (hydrogen / ethylene) respectively, a molar ratio of 0.125% of the autoclave gas phase portion at the time immediately before the polymerization is stopped and the polymerization initiator 10 minutes after, and 0.087% were additionally supplied 1- hexene amount was 2.0mL. Thus resulting ethylene-based polymer was 20.3 g. The analytical results of the polymerization results and the polymer thus obtained are shown in Table 1b.

[Example 2b]
Except for using 30.5mg metallocene compound 22 in place of producing the metallocene compound 21 ethylene polymer using a solid catalyst obtained in the same manner as in (1) of Example 1b, in the conditions shown in Table 1b , by the same method as (2) of example 1b, it was produced ethylene polymer.
Thus resulting ethylene-based polymer was 43.3 grams. The results are shown in Table 1b.

[Example 3b]
(1) except that the metallocene compound 27 in place of the solid catalyst of Preparation metallocene compound 21 using 22.4mg in the same manner as (1) of Example 1b were prepared of the solid catalyst.

(2) to produce ethylene-1-hexene copolymer with the solid catalyst obtained in Production of Ethylene-1-hexene copolymer (1).
That is, heated 2-liter stainless steel autoclave having a stirrer and a temperature controller, thoroughly dried and 50 grams of polyethylene pellets deoxygenated triethyl aluminum to 0.20mmol introduced with stirring 75 ° C. did. After a 1-hexene 1.5ml and ethylene partial pressure was introduced until 1.4 MPa, it was pressed to 90 minutes polymerization 80 mg of the solid catalyst with nitrogen gas.
Incidentally, the polymerization reaction was carried out additional supply of proportional at a feed rate of 1-hexene to ethylene consumption rate. As a result, 0.065% H 2 / C 2 ( hydrogen / ethylene) molar ratio of the autoclave gas phase portion of the polymerization initiator 10 minutes after the polymerization termination immediately before respectively, 0.076% was additionally supplied 1- hexene amount was 5.5mL.
As a result, 35.0 g of polyethylene was produced. The polymerization results are summarized in Table 1b.

[Example 4b]
The preparation metallocene compounds 11 of the ethylene-based polymer using a 9.1 mg, except that the metallocene compound 27 using 35.9mg by using the solid catalyst obtained in the same manner as (1) of Example 3b, Table at 1b conditions, in the same manner as in example 3 (2) was prepared ethylene polymer.
Thus resulting ethylene-based polymer was 28.5 grams. The results are shown in Table 1b.

Example 5b]
Except for using 50.3mg metallocene compound 28 in place of producing the metallocene compound 27 ethylene polymer using a solid catalyst obtained in the same manner as in (1) of Example 4b, under the conditions of Table 1b , by the same method as (2) of example 4b, it was prepared an ethylene-based polymer.
Incidentally, with H 2 before the start of polymerization 250mL and 1-hexene was added 1.5 ml, further in the polymerization reaction was carried out additional supply of H 2 and 1-hexene at a delivery rate proportional to the ethylene consumption rate.
Thus resulting ethylene-based polymer was 42.0 grams. The results are shown in Table 1b.

Comparative Example 1b]
The preparation metallocene compounds 11 of the ethylene-based polymer using 45.5 mg, except for not using a metallocene compound 27 using (1) and obtained in the same manner the solid catalyst of Example 3b, Table 1b under conditions, in the same manner as (2) of example 3b, it was produced ethylene polymer.
Thus resulting ethylene-based polymer was 49.5 grams. The results are shown in Table 1b.

Comparative Example 2b]
Without the preparation metallocene compound 11 of the ethylene-based polymer, except that the metallocene compound 27 using 44.9mg by using the solid catalyst obtained in the same manner as (1) of Example 3b, the conditions of Table 1b at the same manner as (2) of example 3b, it was produced ethylene polymer.
Thus resulting ethylene-based polymer was 22.5 grams. The results are shown in Table 1b.

[Comparative Example 3b]
At ethylene polymer of the manufacturing table 1b conditions, by the same method as in the comparative example 2b, were produced ethylene polymer.
Thus resulting ethylene-based polymer was 44.5 grams. The results are shown in Table 1b.

Figure JPOXMLDOC01-appb-T000094

As shown in Table 1b, the component (A-1b) metallocene compound 11 only resulting ethylene-based polymer, despite the low hydrogen polymerization conditions as in Comparative Example 1b, is to lower the MFR sufficient or difficult, W C value is small and the component (a-2b) metallocene compound 27 only resulting ethylene-based polymer of the comparative example 2b, the g C 'value as in Comparative example 3b or as large as about 0.6 or more, lambda max (2.0) and λ max (2.0) / λ max (0.1) obtained only thing is small, improvement in moldability can not be expected. On the other hand, as the ethylene polymer obtained by the same vapor phase polymerization method using both of the metallocene compound 11 and a metallocene compound 27 is in the embodiment 3b, λ max (2.0), λ max (2 .0) / λ max (0.1) , g C ' value, the W C value is greater both, has a ethylene polymer long chain branched structure is well developed, moldability is improved it can be seen that you are. The ethylene-based polymer of Example 4b obtained by increasing the metallocene compound 27 by reducing the metallocene compound 11, rather than Example 3b, λ max (2.0), λ max (2.0) / λ max (0.1), g C 'value, W C value is small, although the development of long chain branching structure is rather small, excellent moldability than the ethylene polymer obtained in each of the metallocene alone it can be seen. Further, the ethylene polymers of Examples 5b using a metallocene compound 28 as a different component (A-2b), the example 4b about the same lambda max and (2.0) / λ max (0.1 ) g while maintaining the C 'value, W C value is greatly improved. Similarly, using different components (A-2b) as a metallocene compound 21 and metallocene compound 22, Example 1b was carried out slurry polymerization method, also ethylene polymer of Example 2b, λ max (2.0), λ max (2.0) / λ max (0.1), W C value is sufficiently large and the g C 'value indicates a sufficiently small value, useful long chain branched structure to the improvement of molding properties It was found to contain.

Example 6b]
The metallocene compound 12 in place of producing the metallocene compound 11 ethylene polymer using 37.1 mg, except that the metallocene compound 27 using 4.5mg was obtained in the same manner as (1) of Example 3b solid with a catalyst, under the conditions shown in Table 2b, in the same manner as (2) of example 3b, it was produced ethylene polymer.
Thus resulting ethylene-based polymer was 38.5 grams. The results are shown in Table 2b.

[Example 7b]
Except that the metallocene compound 29 in place of producing the metallocene compound 27 of the ethylene-based polymer using 4.3mg by using the solid catalyst obtained in the same manner as in Example 6b, ethylene polymer under conditions of Table 2b It was prepared.
Thus resulting ethylene-based polymer was 31.0 grams. The results are shown in Table 2b.

[Comparative Example 4b]
The preparation metallocene compounds 12 of the ethylene-based polymer using 41.3 mg, except for not using a metallocene compound 27 using the solid catalyst obtained in the same manner as in Example 6b, ethylene at the conditions in Table 2b to produce a system polymer.
Thus resulting ethylene-based polymer was 31.0 grams. The results are shown in Table 2b.

Comparative Example 5b]
At ethylene polymer of the manufacturing table 2b condition, by the same method as Comparative Example 4b, it was prepared an ethylene-based polymer.
Thus resulting ethylene-based polymer was 42.5 grams. The results are shown in Table 2b.

Example 8b]
The metallocene compound 13 in place of producing the metallocene compound 11 ethylene polymer using 39.1 mg, except that the metallocene compound 25 in place of the metallocene compound 21 using 1.5mg in the same manner as in Example 1b (1) using a solid catalyst was collected using, under the conditions of Table 2b, in the same manner as in example 1b (2), to produce ethylene polymer.
Incidentally, with H 2 before the start of polymerization 100mL and 1-hexene was added 40 ml, further in the polymerization reaction was carried out additional supply of H 2 and 1-hexene at a delivery rate proportional to the ethylene consumption rate.
Thus resulting ethylene-based polymer was 48.5 grams. The results are shown in Table 2b.

Example 9b]
At ethylene polymer of the manufacturing table 2b condition, by a method similar to Example 8b, to produce ethylene polymer.
Thus resulting ethylene-based polymer was 48.5 grams. The results are shown in Table 2b.

Example 10b]
Using a solid catalyst obtained in Example 8b of the ethylene-based polymer, under the conditions shown in Table 2b, in the same manner as in Example 3b (2), to produce ethylene polymer.
Incidentally, of H 2 to 370mL and 1-hexene was added 1.5ml before the polymerization initiator, further during the polymerization reaction was carried out additional supply of H 2 and 1-hexene at a delivery rate proportional to the ethylene consumption rate.
Thus obtained ethylene polymer was 8.5 grams. The results are shown in Table 2b.

Comparative Example 6b]
The preparation metallocene compounds 13 of the ethylene-based polymer using 39.9 mg, except for not using a metallocene compound 25 using the solid catalyst obtained in the same manner as in Example 8b, ethylene at the conditions in Table 2b to produce a system polymer.
Thus resulting ethylene-based polymer was 31.4 grams. The results are shown in Table 2b.

Example 11b]
Except that the metallocene compound 14 in place of producing the metallocene compound 12 of the ethylene-based polymer using 40.9mg by using the solid catalyst obtained in the same manner as in Example 6b, ethylene polymer under conditions of Table 2b It was prepared.
Incidentally, with H 2 before the start of polymerization 60mL and 1-hexene was added 1.5 ml, further in the polymerization reaction was carried out additional supply of H 2 and 1-hexene at a delivery rate proportional to the ethylene consumption rate.
Thus resulting ethylene-based polymer was 59.0 grams. The results are shown in Table 2b.

Example 12b]
The metallocene compound 15 in place of producing the metallocene compound 14 of the ethylene-based polymer using 35.9 mg, except that the metallocene compound 27 using 9.0mg by using the solid catalyst obtained in the same manner as in Example 11b , it was produced ethylene polymer under the conditions shown in Table 2b.
Thus resulting ethylene-based polymer was 30.5 grams. The results are shown in Table 2b.

Figure JPOXMLDOC01-appb-T000095

Table 2b, book and components used in Table 1b (A-1b) a metallocene compound 12-15 is another metallocene, in combination with the metallocene compound 27 etc. used as ingredients in Table 1b (A-2b) It shows the results of the olefin polymerization catalyst of the invention. These resulting ethylene-based polymer λ max (2.0), λ max (2.0) / λ max (0.1), g C ' value, W C value, the component (A-1b) alone it is better than when it was found by comparing Comparative example 4b, and Comparative example 6b.

Example 13b]
The metallocene compound 16 in place of producing the metallocene compound 11 ethylene polymer using 36.4 mg, except that the metallocene compound 22 in place of the metallocene compound 21 using 6.1mg are obtained analogously to Example 1b by using the solid catalyst was prepared ethylene polymer under the conditions shown in Table 3b.
Thus resulting ethylene-based polymer was 11.0 grams. The results are shown in Table 3b.

Example 14b]
Except that the metallocene compound 23 in place of producing the metallocene compound 22 of the ethylene-based polymer using 6.8mg by using the solid catalyst obtained in the same manner as in Example 13b, ethylene polymer under conditions of Table 3b It was prepared.
Thus resulting ethylene-based polymer was 30.0 grams. The results are shown in Table 3b.

Example 15b]
Except that the metallocene compound 24 in place of producing the metallocene compound 22 of the ethylene-based polymer using 8.5mg by using the solid catalyst obtained in the same manner as in Example 13b, ethylene polymer under conditions of Table 3b It was prepared.
Thus resulting ethylene-based polymer was 20.0 grams. The results are shown in Table 3b.

Example 16b]
It was produced ethylene polymer in the same manner as in Example 15b in terms of manufacturing table 3b of the ethylene-based polymer.
Thus resulting ethylene-based polymer was 16.5 grams. The results are shown in Table 3b.

Example 17b]
Except that the metallocene compound 16 in place of producing the metallocene compound 11 ethylene polymer using 20.2mg by using the solid catalyst obtained in the same manner as Example 3b, ethylene polymer under conditions of Table 3b It was prepared.
Thus resulting ethylene-based polymer was 46.5 grams. The results are shown in Table 3b.

[Comparative Example 7b-1]
The preparation metallocene compounds 16 of the ethylene-based polymer using 40.5 mg, except for not using a metallocene compound 27 using the solid catalyst obtained in the same manner as in Example 17b, the ethylene under the conditions shown in Table 3b to produce a system polymer.
Thus resulting ethylene-based polymer was 42.0 grams. The results are shown in Table 3b.

Comparative Example 7b-2]
The preparation metallocene compounds 16 of the ethylene-based polymer using 12.1 mg, except for using 39.0mg metallocene compound 31 in place of the metallocene compound 22 using the solid catalyst obtained in the same manner as in Example 13b , it was produced ethylene polymer under the conditions shown in Table 3b.
Thus resulting ethylene-based polymer was 13.5 grams. The results are shown in Table 3b.

Figure JPOXMLDOC01-appb-T000096

Table 3b, and metallocene compounds 16 are different metallocenes and components used in Table 1b and Table 2b (A-1b), components of Table 1b (A-2b) metallocene compound is used as a 22, a metallocene compound 27 such It shows the results of the olefin polymerization catalyst of the present invention in combination with. These resulting ethylene-based polymer λ max (2.0), λ max (2.0) / λ max (0.1), g C ' value, W C value, a component (A-1b) to be better than when using certain metallocene compound 16 alone was found by comparison with comparative example 7b.

Example 18b]
The metallocene compound 17 in place of producing the metallocene compound 11 ethylene polymer using 33.1 mg, except that the metallocene compound 22 in place of the metallocene compound 21 using 3.1mg are obtained analogously to Example 1b by using the solid catalyst was prepared ethylene polymer under the conditions shown in Table 4b.
Thus resulting ethylene-based polymer was 85.8 grams. The results are shown in Table 4b.

Example 19b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 34.5 mg, except using 0.8mg of the metallocene compound 25 in place of the metallocene compound 22 using the solid catalyst obtained in the same manner as in Example 18b , it was produced ethylene polymer under the conditions shown in Table 4b.
Thus resulting ethylene-based polymer was 49.5 grams. The results are shown in Table 4b.

Example 20b]
Using a solid catalyst obtained in Example 19b of the ethylene-based polymer, under the conditions shown in Table 4b, in the same manner as (2) of Example 3b, it was produced ethylene polymer.
Thus resulting ethylene-based polymer was 25.5 grams. The results are shown in Table 4b.

Example 21b]
At ethylene polymer production Table 4b conditions, by the same method as in Example 20b, was produced ethylene polymer.
Thus resulting ethylene-based polymer was 23.5 grams. The results are shown in Table 4b.

Example 22b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 32.4 mg, except that the metallocene compound 26 in place of the metallocene compound 25 using 3.5mg by using the solid catalyst obtained in the same manner as in Example 20b , it was produced ethylene polymer under the conditions shown in Table 4b.
Thus resulting ethylene-based polymer was 22.9 grams. The results are shown in Table 4b.

Example 23b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 32.4 mg, except using 3.1mg of the metallocene compound 27 in place of the metallocene compound 22 using the solid catalyst obtained in the same manner as in Example 18b , it was produced ethylene polymer under the conditions shown in Table 4b.
Thus resulting ethylene-based polymer was 72.0 grams. The results are shown in Table 4b.

Example 24b]
At ethylene polymer production Table 4b conditions, by the same method as in Example 23b, was produced ethylene polymer.
Thus resulting ethylene-based polymer was 47.1 grams. The results are shown in Table 4b.

Example 25b]
At ethylene polymer production Table 4b conditions, by the same method as in Example 23b, was produced ethylene polymer.
Thus resulting ethylene-based polymer was 100.2 grams. The results are shown in Table 4b.

Example 26b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 33.5 mg, except for the metallocene compound 27 using 1.8mg by using the solid catalyst obtained in the same manner as in Example 24b, the conditions of Table 4b It was produced ethylene polymer Te.
Thus resulting ethylene-based polymer was 29.0 grams. The results are shown in Table 4b.

Example 27b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 33.8 mg, except that the metallocene compound 28 in place of the metallocene compound 25 using 1.9mg by using the solid catalyst obtained in the same manner as in Example 20b , it was produced ethylene polymer under the conditions shown in Table 4b.
Thus resulting ethylene-based polymer was 40.0 grams. The results are shown in Table 4b.

Comparative Example 8b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 34.8 mg, except for not using a metallocene compound 25 using the solid catalyst obtained in the same manner as in Example 20b, the ethylene under the conditions shown in Table 4b to produce a system polymer.
Thus resulting ethylene-based polymer was 56.8 grams. The results are shown in Table 4b.

Comparative Example 9b]
The preparation metallocene compounds 17 of the ethylene-based polymer using 34.8 mg, except for not using a metallocene compound 22 using the solid catalyst obtained in the same manner as in Example 18b, the ethylene under the conditions shown in Table 4 to produce a system polymer.
Thus resulting ethylene-based polymer was 14.5 grams. The results are shown in Table 4b.

Comparative Example 10b]
Under conditions of manufacture Table 4b of the ethylene-based polymer, in the same manner as in Comparative Example 9b, was produced ethylene polymer.
Thus resulting ethylene-based polymer was 79.4 grams. The results are shown in Table 4b.

Comparative Example 11b]
The preparation metallocene compounds 27 of the ethylene-based polymer using 44.9 mg, except for not using a metallocene compound 17 using the solid catalyst obtained in the same manner as in Example 23b, the ethylene under the conditions shown in Table 4b to produce a system polymer.
Thus resulting ethylene-based polymer was 54.9 grams. The results are shown in Table 4b.

Comparative Example 12b]
Under conditions of manufacture Table 4b of the ethylene-based polymer, in the same manner as Comparative Example 11b, it was produced ethylene polymer.
Thus resulting ethylene-based polymer was 37.2 grams. The results are shown in Table 4b.

Comparative Example 13b]
Except that the metallocene compound 30 in place of producing the metallocene compound 27 of the ethylene-based polymer was used 41.8mg in the same manner as in Comparative Example 11b, it was produced ethylene polymer under the conditions shown in Table 4b.
Thus resulting ethylene-based polymer was 129.6 g. The results are shown in Table 4b.

Figure JPOXMLDOC01-appb-T000097

Table 4b, and metallocene compounds 17 are different metallocenes and components used in Table 1b ~ Table 3b (A-1b), metallocene compounds were used as ingredients in Table 1b (A-2b) 22, a metallocene compound 25, metallocene compounds 27 shows the results of the olefin polymerization catalyst of the present invention in combination with the metallocene compound 28 like. These resulting ethylene-based polymer λ max (2.0), λ max (2.0) / λ max (0.1), g C ' value, W C value, a component (A-1b) to be better than when using a metallocene compound 27 is located metallocene compound 17 and component (a-2b) alone, it was found by comparing with Comparative example 8b ~ Comparative example 12b. Furthermore, even superior to the long chain branching structure ethylenebis indenyl zirconium are known to impart dichloride ethylene polymers obtained by using the (metallocene compound 30), ethylene heavy obtained in the present invention towards coalescence λ max (2.0) / λ max (0.1), g C ' value, that W C value has a more favorable value, it is clear in comparison with Comparative example 13 it was over.

Example 28b]
With an ethylene-based polymer synthesized solid catalyst in Production Example 6b of, it was produced ethylene polymer under conditions of Table 5b. That is, prepare the molar ratio of 1-hexene / ethylene 0.007, hydrogen / ethylene molar ratio 2.5 × 10 -3, the nitrogen concentration of 30 mol%, the total pressure 0.8 MPa, a temperature of 75 ° C. is a gas phase continuous polymerization apparatus (inner volume 100L, fluidized bed diameter 10 cm, a fluidized bed type polymer - (dispersing agent) 1.5 kg) fed to the triethylaluminum hexane solution (0.03 mmol / ml) in 7 ml / h and, while maintaining the gas composition and temperature constant, the production amount per hour polymerization was carried out intermittently supplying the solid catalyst to be about 300 g. Activity was 336g / (g catalyst · h). The results are shown in Table 5b.

Example 29b]
In the same manner as in the production example 28b of the ethylene-based polymer, to produce a ethylene polymer under conditions of Table 5. The results are shown in Table 5b.

Example 30b]
Except for the preparation polymerization temperature of the ethylene-based polymer and 65 ° C. in the same manner as in Example 28b, it was produced ethylene polymer under conditions of Table 5b. The results are shown in Table 5b.

Example 31b]
Except that 6.3mg using a metallocene compound 28 in place of producing the metallocene compound 27 of ethylene polymer in the same manner as in Example 30b, it was produced ethylene polymer under conditions of Table 5b. The results are shown in Table 5b.

Comparative Example 14b]
Ethylene polymer (2) of Example 1a of the ethylene-based polymer (a) MFR0.8g / 10 min produced and in the same (B-1), ethylene density 0.914 g / cm 3 Weight to give the union. The results are shown in Table 5b. Furthermore while continuing the continuous operation for the production of ethylene polymer having a low density, it was increased from hexene / ethylene molar ratio 0.012, were not newly added hydrogen as molecular weight modifier Nevertheless, MFR begins to increase with 0.8 g / 10 min time, it has been difficult to produce an ethylene polymer having a low MFR and low density as in the above examples 29 b ~ example 31b.

Figure JPOXMLDOC01-appb-T000098

(I) [Synthesis of metallocene compound]
Metallocene compound A: dimethylsilylene (4- (4-trimethylsilyl-phenyl) - - indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (1-1) 4- (4-trimethylsilyl-phenyl) - - Synthesis 500ml flask indene , 4-trimethylsilyl-phenyl boronic acid 10.0g after a solution added (51.5 mmol) and Jimetoetan 200 ml, potassium phosphate 27.3 g (128 mmol), water 100 ml, 4-bromo-indene 8.37 g (43.0 mmol) triphenylphosphine 0.22g (0.86mmol), PdCl 2 ( PPh 3) 2 was added 0.300g of (0.430 mmol) in that order, and stirred under reflux for 12 hours. It was added 100ml of water and cooled to room temperature. The organic phase was separated and the aqueous phase was extracted twice with ethyl acetate 100 ml, and mixed the resultant organic phase was washed with brine and the organic phase was dried with sodium sulfate added thereto. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and purified by silica gel column, 4- (4-trimethylsilyl-phenyl) - - to give a yellow liquid 9.0 g (79% yield) of indene.

(1-2) (4- (4-trimethylsilyl-phenyl) - - indenyl) Synthesis 200ml flask (cyclopentadienyl) dimethylsilane, 4- (4-trimethylsilyl-phenyl) - - indene 16.2 g (61.2 mmol ) and after the added solution 100 ml of THF, cooled to -78 ° C. n-butyl lithium / hexane solution (2.5M) 29.4ml (173.5mmol) was added, and the mixture was stirred for 4 hours returned to room temperature. And dimethyldichlorosilane 14.8 ml (122 mmol) and added THF20ml solution 300ml flask prepared separately, was added to the previous reaction solution was cooled to -78 ° C.. It was stirred for 12 hours returned to room temperature. Volatiles yellow solution 21.8g was obtained with removing by removed by distillation under reduced pressure. The yellow solution was added with THF80ml a solution, CPNA / THF solution (2M) 36.7ml (73.5mmol) was added at -30 ° C.. And stirred for 1 hour to warm to room temperature, ice water was added 100 ml. And extracted twice with ethyl acetate 100 ml, and mixed the resultant organic phase was washed with brine and the organic phase was dried with sodium sulfate added thereto. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and purified by silica gel column, (4- (4-trimethylsilyl-phenyl) - - indenyl) yellow liquid 12.0 g (yield of (cyclopentadienyl) dimethylsilane 51%) was obtained.

(1-3) dimethylsilylene (4- (4-trimethylsilyl-phenyl) - - indenyl) Synthesis 300ml flask (cyclopentadienyl) zirconium dichloride, (4- (4-trimethylsilyl-phenyl) indenyl) (cyclopentadienyl ) dimethylsilane 1.20 g (3.00 mmol), was added diethyl ether 20 ml, and cooled to -70 ° C.. Here it was added dropwise 2.5 mol / L of n- butyllithium -n- hexane solution 2.60 ml (6.60 mmol). After the addition, the mixture was stirred for 2 h to return to room temperature. The solvent of the reaction solution was distilled off under reduced pressure, dichloromethane was added 30 ml, dry ice - cooled to -70 ° C. methanol bath. There were added zirconium tetrachloride 0.770 g (3.30 mmol). Then, gradually and stirred overnight while returning to room temperature. The reaction solution by distilling off the solvent under reduced pressure from the filtrate obtained by filtration, a yellow powder was obtained gills. The powder was recrystallized from toluene 10 ml, 0.500 g (31% yield) of dimethylsilylene (4- (4-trimethylsilyl-phenyl) indenyl) (cyclopentadienyl) zirconium dichloride as yellow crystals was obtained.
1 H-NMR value (CDCl 3): δ0.21 (s , 3H), δ0.23 (s, 9H), δ0.43 (s, 3H), δ5.48 (m, 1H), δ5.51 ( m, 1H), δ5.81 (d, 1H), δ6.60 (m, 1H), δ6.66 (m, 1H), δ6.95 (dd, 1H), δ7.13 (s, 1H), δ7.39 (dd, 2H), δ7.57 (d, 2H), δ7.95 (d, 2H).

Metallocene compound B: dimethylsilylene (4- (4-chloro - phenyl) - indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (2-1) 4- (4-chloro - phenyl) - Synthesis of indene 4- ( 4-trimethylsilyl-phenyl) - - with 4-chlorophenyl boronic acid in place of synthesized 4- trimethylsilylphenyl acid indene performs synthesized by the same procedure as the metallocene compound a (1-1), 4- (4- chloro - phenyl) - indene of white solid was obtained in 69% yield.

(2-2) (4- (4-chloro - phenyl) - indenyl) (cyclopentadienyl) Synthesis of dimethyl silane 4- (4-trimethylsilyl-phenyl) - - instead of 4- (4-chloro indene - phenyl ) - used indene, (performs synthesized by the same procedure as 1-2), (4- (4-chloro - phenyl) - metallocene compound a indenyl) (a pale yellow solid cyclopentadienyl) dimethylsilane Osamu It was obtained at a rate of 52%.

(2-3) dimethylsilylene (4- (4-chloro - phenyl) - indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (4- (4-trimethylsilyl-phenyl) indenyl) (cyclopentadienyl) dimethylsilane Alternatively (4- (4-chlorophenyl) indenyl) using (cyclopentadienyl) dimethylsilane, performs synthesized by the same procedure as the metallocene compound a (1-3), dimethylsilylene (4- (4-chloro - phenyl) - indenyl) (obtained cyclopentadienyl) zirconium dichloride as yellow crystals.
1 H-NMR value (CDCl 3): δ0.87 (s , 3H), δ1.08 (s, 3H), δ5.89 (m, 1H), δ5.94 (m, 1H), δ6.24 ( d, 1H), δ6.78 (m, 1H), δ6.84 (m, 1H), δ7.12 (d, 1H), δ7.19 (dd, 1H), δ7.39 (d, 1H), δ7.44 (m, 3H), δ7.61 (d, 2H).

Metallocene compound C: dimethylsilylene (4- (2- (5-methyl) - furyl) - indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (3-1) 4- (2- (5-methyl) - furyl ) - synthesis 500ml flask indene, after a 2-methylfuran 2.52 g (30.7 mmol) and added THF30ml solution, cooled to -78 ° C. n-butyl lithium / hexane solution (2.5M) 14 .7ml the (36.9 mmol) was added and stirred for 4 hours returned to room temperature. A suspension added THF10ml zinc chloride 4.18 g (30.7 mmol) in 300ml flasks prepared separately, was added to the previous reaction solution was cooled to 0 ° C.. And stirred for 1 hour to warm to room temperature. Further copper iodide in prepared separately ml flask (I) 0.35g (1.84mmol), Pd (dppf) Cl 2 0.690g (0.932mmol), 4- bromo-indene 3.00g and (15.3 mmol) a suspension added DMA5ml, was stirred under reflux by adding the previous reaction solution for 15 hours. Was added 50ml of water was cooled to room temperature. The organic phase was separated and the aqueous phase was extracted twice with ethyl acetate 50 ml, and mixing the resulting organic phase washed twice with water 50 ml, was washed once with brine 50 ml, the organic phase was added sodium sulfate the dried. The sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and purified by silica gel column, 4- (2- (5-methyl) - furyl) - indene yellow solution 2.10 g (70% yield) .

(3-2) (4- (2- (5-methyl) - furyl) - indenyl) Synthesis of (cyclopentadienyl) dimethylsilane 4- (4-trimethylsilyl-phenyl) - - instead of indene 4- (2 - (5-methyl) - furyl) - with indene, (performs synthesized by the same procedure as 1-2), (4- (2- (5-methyl) - furyl) - metallocene compound a indenyl) (cyclo pentadienyl) pale yellow solid dimethylsilane was obtained in 38% yield.

(3-3) dimethylsilylene (4- (2- (5-methyl) - furyl) - indenyl) Synthesis of (cyclopentadienyl) zirconium dichloride (4- (4-trimethylsilyl-phenyl) indenyl) (cyclopentadienyl ) instead of dimethylsilane (4- (2- (5-methyl) - furyl) - indenyl) (using cyclopentadienyl) dimethylsilane performs synthesized by the same procedure as the metallocene compound a (1-3) dimethylsilylene (4- (2- (5-methyl) - furyl) - indenyl) (cyclopentadienyl) zirconium dichloride was obtained as yellow crystals (25% yield).
1 H-NMR value (CDCl3): δ0.00 (s, 3H), δ0.18 (s, 3H), δ1.79 (s, 3H), δ5.22 (m, 1H), δ5.32 (m , 1H), δ5.64 (m, 1H), δ5.72 (d, 1H), δ6.33 (m, 1H), δ6.35 (m, 1H), δ6.70 (m, 2H), δ6 .82 (d, 1H), δ7.43 (d, 1H), δ7.60 (d, 1H).

Metallocene compound D: dimethylsilylene (4- (4-methoxy - phenyl) - indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (4-1) 4- (4-methoxy - phenyl) - Synthesis of indene 4- ( 4-trimethylsilyl-phenyl) - - with 4-methoxyphenyl boronic acid in place of synthesized 4- trimethylsilylphenyl acid indene performs synthesized by the same procedure as the metallocene compound a (1-1), 4- (4 - methoxy - phenyl) - yellow liquid indene was obtained in 89% yield.

(4-2) (4- (4-methoxy - phenyl) - indenyl) (cyclopentadienyl) Synthesis of dimethyl silane 4- (4-trimethylsilyl-phenyl) - - instead of 4- (4-methoxy indene - phenyl ) - used indene, (performs synthesized by the same procedure as 1-2), (4- (4-methoxy - phenyl) - metallocene compound a indenyl) (yield of a yellow liquid cyclopentadienyl) dimethylsilane It was obtained at 35%.

(2-3) dimethylsilylene (4- (4-methoxy - phenyl) - indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (4- (4-trimethylsilyl-phenyl) indenyl) (cyclopentadienyl) dimethylsilane using (4- (4-methoxyphenyl) indenyl) (cyclopentadienyl) dimethylsilane instead performs synthesized by the same procedure as the metallocene compound a (1-3), dimethylsilylene (4- (4-methoxy - phenyl) - indenyl) (cyclopentadienyl) zirconium dichloride was obtained as yellow crystals (54% yield).
1 H-NMR value (CDCl 3): δ0.86 (s , 3H), δ1.07 (s, 3H), δ3.86 (s, 3H), δ5.88 (m, 1H), δ5.92 ( m, 1H), δ6.22 (d, 1H), δ6.77 (m, 1H), δ6.84 (m, 1H), δ7.00 (d, 2H), δ7.18 (m, 2H), δ7.40 (t, 2H), δ7.61 (d, 2H).

Metallocene compound E: dimethylsilylene (4-phenyl indenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (4- (4-trimethylsilyl-phenyl) indenyl) instead of (4-phenyl indenyl (cyclopentadienyl) dimethylsilane yl) (using cyclopentadienyl) dimethylsilane performs synthesized by the same procedure as the metallocene compound a (1-3), dimethylsilylene (4-phenyl indenyl) (cyclopentadienyl) zirconium dichloride as yellow crystals It was obtained as a.

Metallocene compound F: dimethylsilylene (3-methylindenyl) (cyclopentadienyl) Synthesis of zirconium dichloride (4- (4-trimethylsilyl-phenyl) indenyl) instead of (cyclopentadienyl) dimethylsilane (3 Mechiruinde yl) (using cyclopentadienyl) dimethylsilane performs synthesized by the same procedure as the metallocene compound a (1-3), dimethylsilylene (3-methylindenyl) (cyclopentadienyl) zirconium dichloride as yellow crystals It was obtained as a.

Metallocene compound G: Synthesis of dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride Synthesis of dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, conducted according to the procedure described in Macromolecules 1995,28,3771-3778 It was.

(Example 1-1)
(1) Under Preparation nitrogen atmosphere the solid catalyst, put silica 5g was baked for 5 hours at 600 ° C. in 200ml two-necked flask, and drying under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 0.99 ° C.. Put metallocene compound A68mg under a nitrogen atmosphere 100ml two-necked flask which is separately prepared, and dissolved in dehydrated toluene 13.4 ml. It was stirred Albemarle Corp. 20% methylaluminoxane / toluene solution 8.6ml was added 30 minutes to a toluene solution of the metallocene compound A at room temperature. With heating and stirring entered the 200ml two necked flask vacuum-dried silica in an oil bath at 40 ° C., it was added the total amount of the toluene solution of the metallocene compound A and methylaluminoxane reactant. After stirring for 1 hour at 40 ° C., to obtain a solid catalyst distilled off under reduced pressure and toluene solvent while heating to 40 ° C..

(2) Production of ethylene-1-hexene copolymer (1) was produced ethylene-1-hexene copolymer using the obtained solid catalyst in the preparation of the solid catalyst.
That is, the induction stirring device with 2L autoclave to 1-hexene 30 ml, triethylaluminum 0.20 mmol, hydrogen 200 ml, isobutane 800mL mixture was heated to 75 ° C., maintaining the ethylene partial pressure to 1.4MPa by introducing ethylene . Then, the solid catalyst 123mg obtained in the preparation of the solid catalyst of (1) with pressurized nitrogen, ethylene partial pressure 1.4 MPa, and continued for 60 minutes polymerization keeping the temperature 75 ° C.. Incidentally, the polymerization reaction was carried out additional supply of proportional at a feed rate of 1-hexene to ethylene consumption rate. Additional supply was 1-hexene amount was 16.5mL. The polymerization was stopped by adding ethanol. Ethylene-1-hexene copolymer thus obtained had a 130.3 g. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-2)
Using a solid catalyst 202mg obtained in Example 1-1, 1-hexene 40 ml, and hydrogen 150 ml, except 1-hexene amount were additionally supplied was 9.0 mL, in the same manner as in Example 1-1, It was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 55.0g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-3)
Using a solid catalyst 206mg obtained in Example 1-1, except 1-hexene amount were additionally supplied was 9.0 mL, in the same manner as in Example 1-1, the ethylene-1-hexene copolymer It was produced. As a result, an ethylene-1-hexene copolymer 82.0g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-4)
Using a solid catalyst 217mg obtained in Example 1-1, and the hydrogen 500 ml, except 1-hexene amount were additionally supplied was 6.0 mL, in the same manner as in Example 1-1, an ethylene-1-hexene It was prepared copolymer. As a result, an ethylene-1-hexene copolymer 54.8g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-5)
Using a solid catalyst 204mg obtained in Example 1-1, and the hydrogen 640 ml, except 1-hexene amount were additionally supplied was 5.0 mL, in the same manner as in Example 1-1, an ethylene-1-hexene It was prepared copolymer. As a result, an ethylene-1-hexene copolymer 45.5g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Comparative Example 1-1)
(1) Instead of preparing metallocene compounds A68mg solid catalyst, except for using a metallocene compound E59mg, similarly as in Example 1-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 123mg in Production Example 1-1 Ethylene-1-hexene copolymer, using a solid catalyst 222mg obtained in the preparation of the solid catalyst of the above (1), 1- and hexene 40 ml, except 1-hexene amount were additionally supplied was 13.5 mL, in the same manner as in example 1-1, was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 111.8g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Comparative Example 1-2)
Using a solid catalyst 218mg obtained in Comparative Example 1-1, 1-hexene 70 ml, and hydrogen 20 ml, except 1-hexene amount were additionally supplied was 1.5 mL, in the same manner as in Comparative Example 1-1, It was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 24.0g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Comparative Example 1-3)
(1) Instead of preparing metallocene compounds A68mg solid catalyst, except for using a metallocene compound F52mg, similarly as in Example 1-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 123mg in Production Example 1-1 Ethylene-1-hexene copolymer, using a solid catalyst 236mg obtained in the preparation of the solid catalyst of the above (1), 1- hexene 70 ml, and hydrogen 20 ml, except 1-hexene amount were additionally supplied was 18.0 mL, in the same manner as in example 1-1, was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 146.0g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Comparative Example 1-4)
(1) Instead of preparing metallocene compounds A68mg solid catalyst, except for using a metallocene compound G50mg, similarly as in Example 1-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 123mg in Production Example 1-1 Ethylene-1-hexene copolymer, using a solid catalyst 160mg obtained in the preparation of the solid catalyst of the above (1), 1- hexene 40 ml, and hydrogen 100 ml, except 1-hexene amount were additionally supplied was 7.2 mL, in the same manner as in example 1-1, it was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 31.4g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-6)
(1) Instead of preparing metallocene compounds A68mg solid catalyst, except for using a metallocene compound B64mg, similarly as in Example 1-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 123mg in Production Example 1-1 Ethylene-1-hexene copolymer, using a solid catalyst 233mg obtained in the preparation of the solid catalyst of the above (1), 1- and hexene 40 ml, and hydrogen 100 ml, except 1-hexene amount were additionally supplied was 2.0 mL, in the same manner as in example 1-1, was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 29.2g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-7)
Using a solid catalyst 270mg obtained in Example 1-6, 1-hexene 70 ml, and hydrogen 20 ml, except 1-hexene amount were additionally supplied was 2.5 mL, in the same manner as in Example 1-6, to produce the ethylene-hexene copolymer. As a result, an ethylene-1-hexene copolymer 28.0g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-8)
(1) Instead of preparing metallocene compounds A68mg solid catalyst, except for using a metallocene compound D63mg, similarly as in Example 1-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 123mg in Production Example 1-1 Ethylene-1-hexene copolymer, using a solid catalyst 180mg obtained in the preparation of the solid catalyst of the above (1), 1- hexene 40 ml, and hydrogen 100 ml, except 1-hexene amount were additionally supplied was 9.0 mL, in the same manner as in example 1-1, it was produced ethylene-1-hexene copolymer. As a result, an ethylene-1-hexene copolymer 41.0g was formed. The polymerization results are shown in Table 5a-1 and Table 5a-2.

(Example 1-9)
It was produced 1-butene copolymer by using a solid catalyst obtained in Preparation of Examples 1-1 (1) a solid catalyst.
That is, the 1-liter stainless steel autoclave having a stirrer and a temperature controller, the temperature was raised sufficiently dehydrated and polyethylene pellets deoxygenated 80 g, triethylaluminum to 33mg introduced with stirring 90 ° C.. After the ethylene containing 1-butene 10% by weight partial pressure was introduced until 2.0 MPa, the solid catalyst 53mg was pressed with argon gas, ethylene partial pressure 2.0 MPa, 60 minutes polymerization keeping the temperature 90 ° C. It was continued.
As a result, an ethylene · 1-butene copolymer 14.6g was formed. FR of the resulting copolymer 26.2 and a density of 0.918 g / cm 3. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Example 1-10)
Using a solid catalyst 54mg obtained in Example 1-1, except that hydrogen was added 102ml prior to polymerization initiation, in the same manner as in Example 1-9, was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 10.8g was formed. The FR of the obtained copolymer 13.3, density is 0.930 g / cm 3, terminal double bond was 0.40 pieces / 1000 carbons. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Example 1-11)
Example Using the obtained solid catalyst 104mg 1-1, adding hydrogen 272ml prior to polymerization initiation, ethylene was introduced containing 1-butene 5% by weight in place of the ethylene containing 1-butene 10% by weight, except that polymerized 56 minutes, in the same manner as in example 1-9, it was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 25.8g was formed. FR of the obtained copolymer was 9.6. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Examples 1-12)
Using a solid catalyst 58mg obtained in Example 1-1, except that hydrogen was added 51ml prior to polymerization initiation, in the same manner as in Example 1-9, was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 11.1g was formed. FR of the resultant copolymer was 25.7. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Example 1-13)
Using a solid catalyst 55mg obtained in Example 1-1, except that hydrogen was added 153ml prior to polymerization initiation, in the same manner as in Example 1-9, was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 10.4g was formed. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Comparative Example 1-5)
Instead of the solid catalyst 53mg obtained in Example 1-1, except for using the solid catalyst 60mg obtained in the preparation of (1) a solid catalyst of Comparative Example 1-1, in the same manner as in Example 1-9 , it was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 13.2g was formed. Density of the obtained copolymer with 0.935 g / cm 3, terminal double bonds was 0.30 / 1000 carbon atoms. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Example 1-14)
Using a solid catalyst 205mg obtained in Example 1-6 in place of the solid catalyst 53mg obtained in Example 1-1, except that hydrogen was added 34ml prior to polymerization initiation, in the same manner as in Example 1-9 , it was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 29.1g was formed. Density of the obtained copolymer with 0.936 g / cm 3, terminal double bonds was 0.40 / 1000 carbon atoms. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Example 1-15)
Using a solid catalyst 208mg obtained in Example 1-6 in place of the solid catalyst 53mg obtained in Example 1-1, except that hydrogen was added 17ml prior to polymerization initiation, in the same manner as in Example 1-9 , it was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 25.8g was formed. Density of the obtained copolymer with 0.936 g / cm 3, terminal double bonds was 0.40 / 1000 carbon atoms. The polymerization results are shown in Table 6a-1 and Table 6a-2.

(Example 16)
(1) Instead of preparing metallocene compounds A68mg solid catalyst, except for using a metallocene compound C60mg, similarly as in Example 1-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 53mg in Production Example 1-1 1-butene copolymer, with the (1) solid catalyst 203mg obtained in the preparation of the solid catalyst, the polymerization for 47 minutes except that the in the same manner as in example 1-9, was produced 1-butene copolymer.
As a result, an ethylene · 1-butene copolymer 29.5g was formed. FR of the obtained copolymer was 9.4. The polymerization results are shown in Table 6a-1 and Table 6a-2.

Figure JPOXMLDOC01-appb-T000099

Figure JPOXMLDOC01-appb-T000100

Figure JPOXMLDOC01-appb-T000101

Figure JPOXMLDOC01-appb-T000102

<Evaluation>
As described above, comparison of the results shown in Table 5a-1 and Table 5a-2, when compared with Comparative Example 1-1 to Example 1-1, obtained with a catalyst does not meet the requirements of the metallocene compounds of the present invention in example 1-1, even though the amount of a comonomer 1-hexene is high, because the density of the ethylene-based polymer is not decreased, the catalyst comprising a metallocene compound of the present invention as a catalyst component in the active excellent, and it is clear that an excellent copolymerizability. Furthermore, the same comparative example 1-1, despite the amount of hydrogen is less a chain transfer agent polymerization, MFR of the ethylene-based polymer is not decreased, the molecular weight since no improvement, catalyst comprising a metallocene compound of the present invention as a catalyst component is also apparent that the excellent ability to produce ethylene polymer having a low MFR (high molecular weight). Moreover, a characteristic value indicating a characteristic of the long chain branching to improve the moldability of the resulting ethylene-based polymer [λmax (2.0)] B, [λmax (2.0)] B / [λmax (0. 1)] B, g C ' , any of W C is the embodiment 1-1, in addition to not be inferior to the comparative example 1-1, is smaller -15 ° C. soluble content (W -15) since the olefin polymerization catalyst comprising a metallocene compound of the present invention as a catalyst component, than the ethylene polymer obtained in Comparative example 1-1 using the known Patent Document 4 metallocene compounds E, it is clear that excellent moldability and mechanical properties.

Further, when an experiment was conducted for the production of further ethylene polymer having a reduced density than in Example 1-1, the superiority of the metallocene compounds of the present invention that show that become more apparent, Example 1-2 and is the result of Comparative example 1-2. That is, in Comparative Example 1-2 by the catalyst that does not satisfy the requirements of the metallocene compounds of the present invention, loss of activity due to an increase of a comonomer of 1-hexene, an increase in g C '(i.e. reducing the degree of long chain branching), cold whereas an increase in the extractable content is significant, similar decline of example 1-2 in reduced activity that is observed conducted experiments is suppressed to be larger than that of Comparative example 1-2, and, long chain branches characteristic value is not deteriorated either not been observed an increase in the low temperature elution. Nachi Suwa, catalyst comprising the metallocene compound of the present invention as a catalyst component, polymerization characteristics, the table that superiority was more pronounced in the long chain branching characteristics and low-temperature eluting component amount of the ethylene-based polymer of the activity, etc. looking at the 5a-1 and Table 5a-2 is evident.

Similarly metallocene compounds known in Patent Document 5 F, comparative examples using G 1-3, as compared to the results of Comparative Example 1-4 to Example 1-1 to 1-5, polymerization activity, co polymerizable, high molecular weight performance long chain branching characteristics, in overall performance in light of all of the low-temperature eluting component amount, the metallocene compounds of the present invention is excellent as a catalyst component for the polymerization of olefins is clear.

Further, in Examples 1-6 to 1-8 in Table 5a-1 and Table 5a-2, as the metallocene compounds of the present invention, which is different from that in Example 1-1, the metallocene compound B, and polymerization examples of the metallocene compound D Described. Although metallocene compounds of the present invention than the metallocene compound A, such as Example 1 the effect is small, shows a high polymerization activity, further, large .lambda.max (2) values ​​and λmax (2) / λmax (0.1), small g C 'value, a large W C value shows an excellent long chain branching characteristics typified, since the excellent product characteristics because more W -15 is less expected, it was confirmed that significant .

The metallocene compounds also present invention in a gas phase polymerization in Table 5a-1 and Table 5a-2 are different polymerization processes showed the usefulness of a catalyst comprising a catalyst component, in Table 6a-1 and Table 6a-2 is there. That is, when compared with Comparative Example 1-5 to Example 1-9 to 1-13, Comparative Examples 1-5 obtained by the catalyst that does not satisfy the requirements of the metallocene compounds of the present invention is the comonomer 1-butene usage spite same, since the density of the ethylene-based polymer is higher, the catalyst comprising a metallocene compound of the present invention as a catalyst component is excellent in activity, and it has excellent copolymerizability it is clear. Furthermore, the same comparative example 1-5, despite the same amount of use of hydrogen as a chain transfer agent for polymerization, MFR of the ethylene-based polymer for Examples 1-10 is not decreased, the molecular weight from the not improved, the catalyst comprising a metallocene compound of the present invention as a catalyst component is also apparent that the excellent ability to produce an ethylene-based polymer of a low MFR (high molecular weight). Furthermore, long chain branching characteristic values to improve the moldability of the resulting ethylene-based polymer [λmax (2.0)] B, [λmax (2.0)] B /[λmax(0.1)] B , g C ', any of W C is, examples 1-9 to 1-13 had never inferior to Comparative example 1-5.

Further, in Examples 1-14 to 1-16 in Table 6a-1 and Table 6a-2, as the metallocene compounds of the present invention different from the embodiment 1-9 to 1-13, the metallocene compounds B, metallocene compound C describing the polymerization examples. Also metallocene compounds of the present invention show a high polymerization activity comparable to the metallocene compound A such embodiments 1-10, further large .lambda.max (2) value, λmax (2) / λmax (0.1), a small g C 'values, a large W C value indicates either, since the excellent product properties in formability is expected, it was confirmed that the meaningful.

(II) after synthesizing the synthesized following metallocene compounds of the metallocene compound, it was used as a catalyst component.
[Metallocene compound Synthesis Example 1] (hereinafter, sometimes simply referred to as "metallocene compound A")
Synthesis of dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride was conducted according to the procedure described in Example 1 of Japanese Patent Laid-Open 09-87314 discloses.

[Metallocene compound Synthesis Example 2] (hereinafter, sometimes simply referred to as "metallocene compound E")
Synthesis of dimethylsilylene (3-t-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, J. AM. CHEM. SOC. It was carried out according to the procedure described in 2004,126,2089-2104.

[Metallocene compound Synthesis Example 3] (hereinafter, sometimes simply referred to as "metallocene compound F")
Synthesis of dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride was conducted according to the procedure described in Macromolecules 1995,28,3771-3778.

[Metallocene compound Synthesis Example 4] (hereinafter, sometimes simply referred to as "metallocene compound B")
Synthesis of dimethylsilylene (4-t-butylcyclopentadienyl) (indenyl) hafnium dichloride, was carried out by the same procedure as Synthesis Example 1 using the hafnium tetrachloride.

[Metallocene compound Synthesis Example 5] (hereinafter, sometimes simply referred to as "metallocene compound C")
Synthesis of dimethylsilylene (3-trimethylsilyl cyclopentadienyl) (indenyl) zirconium dichloride, (3-trimethylsilyl cyclopentadienyl) using (indenyl) dimethylsilane in the same manner as Synthesis Example 1, the desired product metallocene was obtained as a mixture of isomers.

[Metallocene compound Synthesis Example 6] (hereinafter, sometimes simply referred to as "metallocene compound D")
Synthesis of isopropylidene (4-t-butylcyclopentadienyl) (indenyl) zirconium dichloride, obtained in the same procedure as (4-t-butylcyclopentadienyl) (indenyl) using dimethyl methane [Synthesis Example 1] to give a metallocene of the desired product as a mixture of isomers.

(Example 2-1)
(1) Under Preparation nitrogen atmosphere the solid catalyst, put silica 5 grams of calcined 5 hours at 600 ° C. in 200ml two-necked flask, and drying under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 0.99 ° C.. Put A57 milligrams metallocene compound under a nitrogen atmosphere 100ml two-necked flask which is separately prepared, and dissolved in dehydrated toluene 13.4 ml. It was stirred Albemarle Corp. 20% methylaluminoxane / toluene solution 8.6ml was added 30 minutes to a toluene solution of the metallocene compound A at room temperature. With heating and stirring entered the 200ml two necked flask vacuum-dried silica in an oil bath at 40 ° C., it was added the total amount of the toluene solution of the metallocene compound A and methylaluminoxane reactant. After stirring for 1 hour at 40 ° C., to obtain a solid catalyst distilled off under reduced pressure and toluene solvent while heating to 40 ° C..

(2) to produce ethylene-1-butene copolymer by using the solid catalyst obtained in the preparation of the solid catalyst prepared above ethylene-1-butene copolymer (1).
That is, the 1-liter stainless steel autoclave having a stirrer and a temperature controller, the temperature was raised sufficiently dehydrated and 80 grams of polyethylene pellets deoxygenated, to triethylaluminum was introduced 33 milligrams stirring 90 ° C. . After the ethylene containing 1-butene 10% by weight partial pressure was introduced until 2.0 MPa, the solid catalyst 50 mg were pressed to 60 minutes polymerization with argon gas.
As a result 20.3 grams of ethylene-1-butene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Comparative Example 2-1)
(1) Instead of preparing metallocene compounds A57 milligrams of a solid catalyst, but with the E51 milligrams resulting metallocene compound in Synthesis Example 2, in the same manner as in Example 2-1 to prepare a solid catalyst.
(2) in place of the solid catalyst 50 mg obtained in Production Example 2-1 1-butene copolymer, using a solid catalyst 56 mg obtained in the preparation of the solid catalyst, a polymerization temperature of 80 ℃ to, except that was carried out 51 minutes polymerization, in the same manner as in example 2-1, was produced 1-butene copolymer.
As a result 25.8 grams of ethylene-1-butene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Example 2-2)
(2) to produce ethylene-1-hexene copolymer using a solid catalyst obtained in Example 2-1 Ethylene-1-hexene copolymer.
That is, 2-liter stainless steel autoclave having a stirrer and a temperature controller, was sufficiently dehydrated and polyethylene pellets deoxygenated and heated to 50g introduced triethylaluminum 0.20mmol stirring 75 ° C. . After a 1-hexene 1.5 ml and the ethylene partial pressure was introduced until 1.4 MPa, it was pressed to 90 minutes polymerization the solid catalyst 64 milligrams nitrogen gas. Incidentally, during the polymerization reaction was carried out additional supply of proportional at a feed rate of 1-hexene to ethylene consumption rate. As a result, 0.093% H 2 / C 2 ( hydrogen / ethylene) molar ratio of the autoclave gas phase portion of the polymerization initiator 10 minutes after the polymerization termination immediately before respectively, 0.104% was additionally supplied 1- hexene amount was 9.5mL. As a result 49.5 grams of ethylene-1-hexene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Comparative Example 2-2)
Instead of the solid catalyst 64 mg obtained in Example 2-1, except for using the solid catalyst 62 mg obtained in the solid catalyst prepared in Comparative Example 2-1, in the same manner as in Example 2-2, ethylene 1-hexene copolymer was produced. However, 1-hexene amount of added supply was 7.5mL. 0.122% H 2 / C 2 (hydrogen / ethylene) molar ratio of the autoclave gas phase portion of the polymerization initiator 10 minutes after the polymerization termination immediately before each was 0.137%. As a result 42.0 grams of ethylene-1-hexene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Comparative Example 2-3)
(1) Instead of preparing metallocene compounds A57 milligrams of a solid catalyst, but with the F50 milligrams metallocene compound obtained in Synthesis Example 3, in the same manner as in Example 2-1 to prepare a solid catalyst.
(2) using a solid catalyst 194 mg was obtained in the preparation of the solid catalyst prepared above ethylene-1-hexene copolymer (1), 1-hexene 10 weight instead of ethylene containing 1-butene 10 wt% % with ethylene containing a except for using 70 ° C. the polymerization temperature in the same manner as in example 2-1, was produced ethylene-1-hexene copolymer.
As a result 13.7 grams of ethylene-1-hexene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Reference Example 2-1)
(2) using a solid catalyst 52 mg obtained in Production Example 2-1 Ethylene-1-hexene copolymer, an ethylene containing 1-hexene 10 weight percent instead of ethylene containing 1-butene 10 wt% except for using, as in example 2-1, it was produced ethylene-1-hexene copolymer.
As a result 17.5 grams of ethylene-1-hexene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Comparative Example 2-4)
(1) Instead of preparing metallocene compounds A57 milligrams of a solid catalyst, but with the G44 milligrams made of metallocene compounds by Wako Pure Chemical Industries, in the same manner as in Example 2-1 to prepare a solid catalyst.
(2) using a solid catalyst 49 mg obtained in the preparation of manufacturing the solid catalyst ethylene-1-hexene copolymer, an ethylene containing 1-hexene 5 wt% in place of the ethylene containing 1-butene 10 wt% except for using, as in example 2-1, it was produced ethylene-1-hexene copolymer.
As a result, 4.5 ethylene-1-hexene copolymer grams was generated. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Comparative Example 2-5)
(1) was produced ethylene polymer using the obtained solid catalyst in the preparation of the solid catalyst prepared in Comparative Example 2-4 ethylene polymer.
That is, the induction stirring device with 2L autoclave isobutane 800 mL, triethylaluminum 0.20mmol addition, the temperature was raised to 75 ° C., maintaining the ethylene partial pressure to 1.4MPa by introducing ethylene. Then, the solid catalyst 525mg of Comparative Example 2-4 was pressurized nitrogen, ethylene partial pressure 1.4 MPa, was continued for 60 minutes polymerization keeping the temperature 75 ° C., ethanol polymerization was quenched by the addition. Polymerization H 2 / C 2 of the autoclave gas phase of the suspension immediately before the time (hydrogen / ethylene) molar ratio was 0.088%. Thus obtained ethylene polymer was 60.0 g. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Example 2-3)
(2) using a solid catalyst 55 mg obtained in Production Example 2-1 1-butene copolymer, the polymerization temperature to 70 ° C., except for performing 31 minutes polymerization, Example 2-1 similar to, and prepared ethylene-1-butene copolymer.
As a result 25.6 grams of ethylene-1-butene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Reference Example 2-2)
(1) Under Preparation nitrogen atmosphere triethylaluminum treated montmorillonite was placed a commercially available montmorillonite 3.0 g in 200ml two-necked flask, and drying under reduced pressure for 1 hour with a vacuum pump while heating in an oil bath at 200 ° C.. After cooling to room temperature, and the slurry was added heptane 75 ml, stirred triethylaluminum with (a concentration of 70 grams / liter of heptane solution) was added 14.4 milliliter. After stirring for 1 hour at room temperature, the solid was washed until 1 dilutions 1/100 by decantation. Finally heptane was added until the liquid volume of 150 ml to obtain a slurry of triethylaluminum-treated montmorillonite.
(2) to produce ethylene-1-hexene copolymer using a triethylaluminum treated montmorillonite Production of Ethylene-1-hexene copolymer (1).
That is, the 1-liter stainless steel autoclave having a stirrer and a temperature controller, thoroughly dehydrated heptane 500ml, triethylaluminum 55 mg, introducing 1-hexene 10 ml raising the agitation 80 ° C. It was allowed. After the ethylene partial pressure was introduced until 1.5 MPa, the triethylaluminum treated montmorillonite 50 milligrams and (heptane slurry 2.5 ml) a metallocene compound A2.5 micromolar conducted pressed to 60 minutes polymerization with argon gas It was. During the polymerization reaction ethylene was introduced containing 1-hexene 10 weight percent depending on the ethylene consumed by the system inside pressure was kept 1.5 MPa.
As a result, 3.0 g of ethylene-1-hexene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Example 2-4)
(1) Instead of preparing metallocene compounds A57 milligrams of a solid catalyst, but with the B68 milligrams resulting metallocene compound in Synthesis Example 2-4, in the same manner as in Example 2-1 to prepare a solid catalyst.
(2) instead of the resulting solid catalyst 50 milligrams Preparation Example 2-1 1-butene copolymer, using a solid catalyst 210 mg was obtained in the preparation of the solid catalyst, hydrogen 34 ml except adding, in the same manner as in example 2-1, was produced 1-butene copolymer.
As a result, 10.0 g of ethylene-1-butene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Example 2-5)
(1) Instead of preparing metallocene compounds A57 milligrams of a solid catalyst, except for using C 59 milligrams metallocene compounds obtained in Synthesis Example 5, in the same manner as in Example 2-1 to prepare a solid catalyst.
(2) in place of the solid catalyst 50 mg obtained in Production Example 2-1 1-butene copolymer, except that the solid catalyst 54 mg obtained in the preparation of the solid catalyst, carried as in example 2-1, it was produced 1-butene copolymer.
As a result 16.5 grams of ethylene-1-butene copolymer was produced. The polymerization results are shown in Table 7a-1 and Table 7a-2.

(Example 2-6)
(1) Instead of preparing metallocene compounds A57 milligrams of a solid catalyst, except for using D 55 milligrams metallocene compound obtained in Synthesis Example 6, in the same manner as in Example 2-1 to prepare a solid catalyst.
(2) to produce ethylene-1-hexene copolymer with the solid catalyst obtained in the preparation of the solid catalyst prepared above ethylene-1-hexene copolymer (1).
That is, the induction stirring device with 2L autoclave isobutane 800 mL, 1-hexene 40 mL, triethylaluminum 0.20mmol addition, the temperature was raised to 75 ° C., maintaining the ethylene partial pressure to 1.4MPa by introducing ethylene.
Then, the solid catalyst 180mg obtained in the above (1) with pressurized nitrogen, ethylene partial pressure 1.4 MPa, was continued for 60 minutes polymerization keeping the temperature 75 ° C., ethanol polymerization was quenched by the addition. Incidentally, the polymerization reaction was carried out additional supply of proportional at a feed rate of 1-hexene to ethylene consumption rate. As a result, the average value of the polymerization initiation of the autoclave gas phase portion at the time after 10 minutes and the polymerization is stopped just before H 2 / C 2 (hydrogen / ethylene) molar ratio is 0.098% additionally supplied with 1-hexene amount was 12mL. Thus resulting ethylene-based polymer was 48.5 g. The polymerization results are shown in Table 7a-1 and Table 7a-2.

Figure JPOXMLDOC01-appb-T000103

Figure JPOXMLDOC01-appb-T000104

As described above, from the results shown in Table 7a-1 and Table 7a-2, and Comparative Example 2-1 to Example 2-1, also when compared with Comparative Example 2-2 to Example 2-2, Comparative example obtained in the catalyst that does not satisfy the requirements of the metallocene compounds of the present invention 2-1, the ethylene polymer shown in Comparative examples 2-2, the requirement (B-4'-i) [λmax (2.0 )] [λmax (2.0 in B and requirements (B-4'-ii)) ] B /[λmax(0.1)] or are inferior B, g C requirements (B-4'-iii) 'it is or not small enough, or have poor W C requirements (B-4'-iv). From these, the ethylene-based polymer prepared in Example according to the present invention it is clear that excellent moldability.
Further, Table 7a-1 and Table 7a-2 of Example 2-1, as compared to the polymerization activity of Example 2-2, the requirements of the metallocene compounds of the present invention as in Comparative Examples 2-3 ~ Comparative Example 2-5 the polymerization activity of ethylene polymerization by the catalyst that does not satisfy the, since very low, it is clear that there is a problem in economical efficiency as a method for producing ethylene polymer. Furthermore, the ethylene polymer obtained in this Comparative Example 2-3, it is clear that [λmax (2.0)] for B is too large, only be obtained ethylene polymer having poor strength. Furthermore, the ethylene polymer obtained in this Comparative Example 2-4 and Comparative Example 2-5, the requirements (B-4'-ii) of [λmax (2.0)] B /[λmax(0.1 )] B is inferior. From these, the ethylene-based polymer prepared in Example of the present invention is excellent in formability, it is clear that further is excellent in economical efficiency.

In Examples 2-4 to Example 2-6 of Table 7a-1 and Table 7a-2 satisfies the requirements of the metallocene compounds of the present invention used in Examples 2-1 to 2-3 Catalyst an example of using a metallocene compound having a structure different from that of the.
Metallocene compound of Example 2-4, the metallocene compound and the central metal species of Examples 2-1 is only different from the Hf and Zr, the ligand has the same structure, in Example 2-1, inferior to the active, W C of the requirements of the present invention (B-4'-iv) have a relatively large value, the ethylene polymer is expected to be excellent moderately moldability.
Metallocene compound of Example 2-5, the substituents on the metallocene compound and the cyclopentadienyl ring of Examples 2-1 are only different from the trimethylsilyl group and t- butyl group, the other has the same structure have example 2-1 similar high activity, requirement (B-4'-i) of the present invention, that are sufficiently satisfied (B-4'-ii) (B-4'-iv) from the ethylene polymer is excellent formability.
Metallocene compound of Example 2-6, the only bridging group linking the metallocene compound and the cyclopentadienyl ring and the indenyl ring of Example 2-1 is different from the i- propyl group and dimethylsilylene group, others the same structure has, have example 2-1 similar high activity, since it satisfies the requirements of the present invention (B-4'-iv), the ethylene polymer is excellent formability.
From the above, it was shown that ethylene-based polymer produced by the catalyst using a metallocene compound belonging to the present invention is expressed formability were both fully improved.

Has been described with reference to the details to the specific embodiments of the present invention, it is possible that various changes and modifications without departing from the spirit and scope of the invention will be apparent to those skilled in the art. The present application, Japanese patent application filed on March 30, 2011 (Japanese Patent Application No. 2011-073937), and of March 30, 2011 application is based on Japanese patent application (Japanese Patent Application No. 2011-073945), the contents of of which are incorporated herein by reference.

As apparent from the above, the polyethylene resin composition of the present invention is excellent in molding properties, at the same time, excellent in balance between impact strength and rigidity, further has the effect of excellent in transparency, also, the injection molding polyethylene resin composition, compression injection molding, rotational molding, extrusion molding, blow molding or molded article obtained by blow molding also because an excellent balance of impact strength and stiffness and transparency, is thin it is possible to economically provide advantageous molded products.
Therefore, the industrial value of the polyethylene resin composition of the present invention is extremely large, which can provide a molded product having such desirable properties economically advantageously.
Further, by using the olefin polymerization catalyst component of the present invention, the olefin polymer, the olefin polymerization catalyst capable of introducing long chain branching of sufficient number and length are obtained, high-pressure low excellent moldability alternative density polyethylene, chromium-based alternative high-density polyethylene obtained by the catalyst, useful olefin polymers such as moldability improving metallocene polymer. For these reasons, the significance of the olefin polymerization catalyst of the present invention is high, the availability of its industrial is extremely large.

Claims (14)

  1. Ethylene polymer satisfying the following conditions (B-1 ') ~ condition (B-6).
    (B-1 ') MFR B = 0.001 ~ 200g / 10 minutes (B-2 ") Density B = 0.880 ~ 0.970g / cm 3
    (B-3) [Mw / Mn] B = 2.0 ~ 10.0
    (B-4 ') Temperature 170 ° C., elongation strain rate 2 extensional viscosity measured in (in 1 / sec) eta (t) (unit: Pa · sec) and elongation time t (in seconds) log-log plot of in the case where either inflection point of elongational viscosity due to strain hardening is not observed, or the inflection point is observed, the maximum elongation viscosity after strain hardening η B; Max (t 1) , before curing extension when a linear (t), η B; ; the approximate line viscosity eta B is linear (t 1) strain hardening degree which is defined by [λmax (2.0)] B; Max (t 1) / η B it is from 1.2 to 30.0.
    (B-5) above condition (B-4 ') are defined in the same manner as in [λmax (2.0)] B and, when measured in the same manner elongation strain rate of 0.1 (in 1 / sec) of [λmax (0.1)] the ratio of B [λmax (2.0)] B /[λmax(0.1)] B is 1.2 to 10.0.
    (B-6) is a polymer prepared by polymerization of ethylene using a catalyst containing a transition metal.
  2. Ethylene polymer of claim 1, further satisfying at least one of the following conditions (B-7) and condition (B-8).
    (B-7) differential refractometer, viscosity detectors, and branching index of the molecular weight of 1,000,000 determined by GPC measurement device combining a light scattering detector (g C ') is at 0.30 to 0.70 .
    (B-8) differential refractometer, viscosity detectors, and the content of molecular weight of 1,000,000 or more components measured by GPC measurement device combining a light scattering detector (W C) is at 0.01 to 30% is there.
  3. (A) and the ethylene-based polymer 41 to 99% by weight, thereby satisfying the (A-1) ~ condition (A-4) below, (B) according to claim 1 or claim 2 ethylene polymer according to 1 and a ~ 59 wt%, and, MFR of the total composition is 0.05 ~ 50 g / 10 min, polyethylene resin composition density of 0.910 ~ 0.960g / cm 3.
    Conditions of the ethylene-based polymer (A);
    (A-1) MFR A = 0.3 ~ 100g / 10 minutes (A-2) Density A = 0.915 ~ 0.970g / cm 3
    (A-3) [Mw / Mn] A = 2.0 ~ 10.0
    (A-4) Temperature 170 ° C., elongation strain rate 2 extensional viscosity measured in (in 1 / sec) eta (t) (unit: Pa · sec) and elongation time t: the log-log plot of (in seconds) If either inflection point of elongational viscosity due to strain hardening is not observed, or the inflection point is observed, the maximum elongation viscosity after strain hardening η a; Max (t 1) , extensional viscosity before curing when a linear (t), η a; ; approximate line of eta a of Max (t 1) / η a ; linear (t 1) strain hardening degree which is defined by [λmax (2.0)] a 1 it is 1.0 to 2.0.
  4. The ethylene polymer (B) is a polyethylene-based resin composition according to claim 3 which satisfies the following condition (B-1) ~ condition (B-6).
    Conditions of the ethylene-based polymer (B);
    (B-1) MFR B = 0.01 ~ 1.5g / 10 min, and, 100> MFR A / MFR B > 1.0
    (B-2) Density B = 0.880 ~ 0.940g / cm 3
    (B-3) [Mw / Mn] B = 2.0 ~ 10.0
    (B-4) [λmax ( 2.0)] are defined in the same manner as in conditions described (A-4) in claim 3 B is 1.2 to 20.0 and, 20> [.lambda.max (2.0)] B /[λmax(2.0)] a> 1.0.
    (B-5) Similar to [λmax (2.0)] B defined in the same manner as in conditions described (A-4) in claim 3, the extension strain rate of 0.1 (in 1 / sec) it is 1.2 ~ 10.0 [λmax (0.1) ] the ratio of B [λmax (2.0)] B /[λmax(0.1)] B as measured in.
    (B-6) is a polymer prepared by polymerization of ethylene using a catalyst containing a transition metal.
  5. The ethylene polymer (B), the polyethylene resin composition of claim 3, further satisfying the following condition (B-2 ').
    (B-2 ') 1.070> Density A / Density B> 0.990
  6. The ethylene polymer (A), an ethylene polymer or an ethylene-produced by copolymerization of homopolymerization or α- olefins ethylene by Ziegler-Natta catalyst produced using the magnesium compound and a titanium compound α- polyethylene resin composition of claim 3 wherein the olefin copolymer.
  7. Injection molding polyethylene resin composition according to claim 3, compression injection molding, rotational molding, extrusion molding, blow molding or blow molding a molded article to be obtained.
  8. Extruding the polyethylene resin composition according to claim 3, hollow molding, obtained by blow molding or inflation molding film.
  9. Olefin polymerization catalyst component comprising the following component (A-1b) and component (A-2b).
    Component (A-1b): a metallocene compound represented by the following general formula (1b)
    Figure JPOXMLDOC01-appb-C000001
    Wherein (1b), M 1b represents any of the transition metals Ti, Zr or Hf. X 1b and X 2b are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1b and Q 2b are each independently a carbon atom, a silicon atom or a germanium atom. R 1b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four at least two bonded out of R 1b, to form a ring together with Q 1b and Q 2b it may be. m b is 0 or 1, if m b is 0, Q 1b is directly bonded to the conjugated 5-membered ring containing R 2b and R 3b. R 2b, R 3b and R 4b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing an oxygen atom or a sulfur atom. R 2b, of R 3b and R 4b, or one pair of adjacent R 3b each other or adjacent R 2b and R 3b only may form a ring together with the carbon atom bonded. ]
    Component (A-2b): a metallocene compound represented by the following general formula (2b)
    Figure JPOXMLDOC01-appb-C000002
    Wherein (2b), M 2b represents any of the transition metals Ti, Zr or Hf. X 11b and X 12b each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 11b represents a carbon atom, a silicon atom or a germanium atom. R 11b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, two R 11b may form a ring together with Q 11b bonded to each other. R 12b, R 14b and R 15b are each independently hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6 having 1 to 20 carbon atoms, indicates an atom or group selected from halogen-containing hydrocarbon group, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom having 1 to 20 carbon atoms but of them, at least not one hydrogen atom. R 13b are each independently a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1-6, halogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, an oxygen atom or a hydrocarbon group-substituted silyl group or a hydrocarbon group having 1 to 40 carbon atoms having 1 to 40 carbon atoms containing a sulfur atom. R 12b, R 13b, of R 14b and R 15b, between the adjacent R 12b, either one pair of adjacent R 13b together or adjacent R 12b and R 13b only, adjacent R 14b together, adjacent R 15b or between any one pair of adjacent R 14b and R 15b only, they may form a ring together with the bond to which carbon atoms. ]
  10. Olefin polymerization catalyst component comprising a metallocene compound represented by the following general formula (1c).
    Figure JPOXMLDOC01-appb-C000003
    Wherein (1c), M 1c indicates one of the transition metals Ti, Zr or Hf. X 1c and X 2c are each independently hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1c and Q 2c are each independently a carbon atom, a silicon atom or a germanium atom. R 1c are each independently, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four to form a ring together with Q 1c and Q 2c and at least two members out of R 1c it may be. m c is 0 or 1, if m c is 0, Q 1c is directly bonded to the conjugated 5-membered ring containing R 2c. R 2c and R 4c are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms 1 to 6 having 1 to 20 carbon atoms, 1 to 4 carbon atoms halogen-containing hydrocarbon group of 1-20, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom. R 3c represents a substituted aryl group represented by the following general formula (1-ac). ]
    Figure JPOXMLDOC01-appb-C000004
    Wherein (1-ac), Y 1c is the periodic table group 14 shows a group 15 or 16 atom.R 5c, R 6c, R 7c , R 8c and R 9c each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, the number of carbon atoms containing a bromine atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen or nitrogen hydrocarbon group of 1 to 20, a hydrocarbon group-substituted amino group, an alkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms containing silicon atoms from 1 to 6 having 1 to 20 carbon atoms, carbon halogen-containing hydrocarbon group having 1 to 20, or a hydrocarbon group-substituted silyl group having a carbon number of 1 ~ 20, R 5c, R 6c, R 7c, R 8c and R 9c are joined adjacent groups , they may form a ring together with the bonded atoms to them. n c is 0 or 1, if n c is 0, there is no substituent R 5c to Y 1c. p c is 0 or 1, if p c is 0, carbon atoms carbon atoms and R 9c which R 7c is attached is bound is directly attached. If Y 1c is a carbon atom, R 5c, R 6c, R 7c, R 8c, at least one of R 9c is not a hydrogen atom. ]
  11. Olefin polymerization catalyst containing the olefin polymerization catalyst component according to claim 9 or claim 10.
  12. By using an olefin polymerization catalyst comprising the following components (A) and (B), of the conditions of claim 1, ethylene to produce ethylene polymer which satisfies at least condition (B-4 ') method of manufacturing a polymer.
    Component (A): The following catalyst component (A-i) ~ (A-iii) at least one of (A-i) A catalyst component for olefin polymerization according to claim 9 (A-ii) according to claim 10 olefin polymerization catalyst component comprising a metallocene compound represented by the olefin polymerization catalyst component according (a-iii) the following general formula (1d) to
    Figure JPOXMLDOC01-appb-C000005
    Wherein (1d), M 1d represents any of the transition metals Ti, Zr or Hf. X 1d and X 2d are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, 1 to 20 carbon atoms It shows a hydrocarbon group-substituted amino group or an alkoxy group having 1 to 20 carbon atoms. Q 1d and Q 2d are each independently a carbon atom, a silicon atom or a germanium atom. R 1d are each independently, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, four to form a ring together with Q 1d and Q 2d and at least two members out of R 1d it may be. m d is 0 or 1, if m d is 0, Q 1d is directly bonded to the conjugated 5-membered ring containing R 2d and R 3d. R 2d and R 3d is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having silicon atoms 1-1 carbon atoms containing from 6 to 18 halogen containing 1 to 20 carbon atoms hydrocarbon group, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom, not the least one hydrogen atom of R 2d. R 4d represents a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 or 5 to form a fused ring with respect to 5-membered ring bonded. R 5d is an atom or group bonded to the carbon atoms of R 4d, each independently, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 1 containing silicon atoms 1-6 ~ 18 silicon-containing hydrocarbon group, a halogen-containing hydrocarbon group, a hydrocarbon group or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms having 1 to 20 carbon atoms containing an oxygen atom having 1 to 20 carbon atoms. n d represents an integer of 0 to 10, if n d is 2 or more, at least two R 5d, together with binding to that carbon atom may form a ring. ]
    Component (B): a compound which reacts with the metallocene compound to form a cationic metallocene compound of the component (A)
  13. Ethylene-based polymer according to claim 1 manufactured by the manufacturing method of the ethylene polymer according to the claim 12.
  14. The ethylene-based polymer, polyethylene-based resin composition according to claim 3, wherein the ethylene polymer of claim 13.
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